Diels–Alder reaction

In organic chemistry, the Diels–Alder reaction is a chemical reaction Diels–Alder reaction

between a conjugated diene and a substituted alkene, commonly termed
Reaction type Cycloaddition
the dienophile, to form a substituted cyclohexene derivative. It is the
prototypical example of a pericyclic reaction with a concerted Identifiers

mechanism. More specifically, it is classified as a thermally allowed Organic Chemistry diels-alder-reaction

[4+2] cycloaddition with Woodward–Hoffmann symbol [π4s + π2s]. It Portal
was first described by Otto Diels and Kurt Alder in 1928. For the RSC ontology ID RXNO:0000006
discovery of this reaction, they were awarded the Nobel Prize in
Chemistry in 1950. Through the simultaneous construction of two
new carbon–carbon bonds, the Diels–Alder reaction provides a
reliable way to form six-membered rings with good control over the
regio- and stereochemical outcomes.[1][2] Consequently, it has
served as a powerful and widely applied tool for the introduction of
chemical complexity in the synthesis of natural products and new Diels–Alder reaction, simplest example
materials.[3][4] The underlying concept has also been applied to π-
systems involving heteroatoms, such as carbonyls and imines,
which furnish the corresponding heterocycles; this variant is known as the hetero-Diels–Alder reaction. The reaction has
also been generalized to other ring sizes, although none of these generalizations have matched the formation of six-
membered rings in terms of scope or versatility. Because of the negative values of ΔH° and ΔS° for a typical Diels–Alder
reaction, the microscopic reverse of a Diels–Alder reaction becomes favorable at high temperatures, although this is of
synthetic importance for only a limited range of Diels–Alder adducts, generally with some special structural features; this
reverse reaction is known as the retro-Diels–Alder reaction.[5]

Mechanism
The reaction is an example of a concerted pericyclic reaction.[6] It is believed to occur via a single, cyclic transition
state,[7] with no intermediates generated during the course of the reaction. As such, the Diels–Alder reaction is governed
by orbital symmetry considerations: it is classified as a [π4s + π2s] cycloaddition, indicating that it proceeds through the
suprafacial/suprafacial interaction of a 4π electron system (the diene structure) with a 2π electron system (the dienophile
structure), an interaction that leads to a transition state without an additional orbital symmetry-imposed energetic barrier
and allows the Diels–Alder reaction to take place with relative ease.[8]

A consideration of the reactants' frontier molecular orbitals (FMO) makes plain why this is so. (The same conclusion can
be drawn from an orbital correlation diagram or a Dewar-Zimmerman analysis.) For the more common "normal" electron
demand Diels–Alder reaction, the more important of the two HOMO/LUMO interactions is that between the electron-rich
diene's ψ2 as the highest occupied molecular orbital (HOMO) with the electron-deficient dienophile's π* as the lowest
unoccupied molecular orbital (LUMO). However, the HOMO–LUMO energy gap is close enough that the roles can be
reversed by switching electronic effects of the substituents on the two components. In an inverse (reverse) electron-
demand Diels–Alder reaction, electron-withdrawing substituents on the diene lower the energy of its empty ψ3 orbital and
electron-donating substituents on the dienophile raise the energy of its filled π orbital sufficiently that the interaction
between these two orbitals becomes the most energetically significant stabilizing orbital interaction. Regardless of which
situation pertains, the HOMO and LUMO of the components are in phase and a bonding interaction results as can be seen
in the diagram below. Since the reactants are in their ground state, the reaction is initiated thermally and does not require
activation by light.[8]
The "prevailing opinion"[9][10][11][12] is that most Diels–Alder reactions proceed through a concerted mechanism; the
issue, however, has been thoroughly contested. Despite the fact that the vast majority of Diels–Alder reactions exhibit
stereospecific, syn addition of the two components, a diradical intermediate has been postulated[7] (and supported with
computational evidence) on the grounds that the observed stereospecificity does not rule out a two-step addition involving
an intermediate that collapses to product faster than it can rotate to allow for inversion of stereochemistry.

There is a notable rate enhancement when certain Diels–Alder reactions are carried out in polar organic solvents such as
dimethylformamide and ethylene glycol,[13] and even in water.[14] The reaction of cyclopentadiene and butenone for
example is 700 times faster in water relative to 2,2,4-trimethylpentane as solvent.[14] Several explanations for this effect
have been proposed, such as an increase in effective concentration due to hydrophobic packing[15] or hydrogen-bond
stabilization of the transition state.[16]

The geometry of the diene and dienophile components each propagate into stereochemical details of the product. For
intermolecular reactions especially, the preferred positional and stereochemical relationship of substituents of the two
components compared to each other are controlled by electronic effects. However, for intramolecular Diels–Alder
cycloaddition reactions, the conformational stability of the structure of the transition state can be an overwhelming
influence.

Regioselectivity
Frontier molecular orbital theory has also been used to explain the regioselectivity patterns observed in Diels–Alder
reactions of substituted systems. Calculation of the energy and orbital coefficients of the components' frontier orbitals[17]
provides a picture that is in good accord with the more straightforward analysis of the substituents' resonance effects, as
illustrated below.

In general, the regioselectivity found for both normal and inverse electron-demand Diels–Alder reaction follows the ortho-
para rule, so named, because the cyclohexene product bears substituents in positions that are analogous to the ortho and
para positions of disubstituted arenes. For example, in a normal-demand scenario, a diene bearing an electron-donating
group (EDG) at C1 has its largest HOMO coefficient at C4, while the dienophile with an electron withdrawing group
(EWG) at C1 has the largest LUMO coefficient at C2. Pairing these two coefficients gives the "ortho" product as seen in
case 1 in the figure below. A diene substituted at C2 as in case 2 below has the largest HOMO coefficient at C1, giving rise
to the "para" product. Similar analyses for the corresponding inverse-demand scenarios gives rise to the analogous
products as seen in cases 3 and 4. Examining the canonical mesomeric forms above, it is easy to verify that these results
are in accord with expectations based on consideration of electron density and polarization.

In general, with respect to the energetically most well-matched HOMO-LUMO pair, maximizing the interaction energy by
forming bonds between centers with the largest frontier orbital coefficients allows the prediction of the main regioisomer
that will result from a given diene-dienophile combination.[8] In a more sophisticated treatment, three types of substituents
(Z withdrawing: HOMO and LUMO lowering (CF3, NO2, CN, C(O)CH3), X donating: HOMO and LUMO raising (Me,
OMe, NMe2), C conjugating: HOMO raising and LUMO lowering (Ph, vinyl)) are considered, resulting in a total of 18
possible combinations. The maximization of orbital interaction correctly predicts the product in all cases for which
experimental data is available. For instance, in uncommon combinations involving X groups on both diene and dienophile,
a 1,3-substitution pattern may be favored, an outcome not accounted for by a simplistic resonance structure argument.[18]
However, cases where the resonance argument and the matching of largest orbital coefficients disagree are rare.

Stereospecificity and stereoselectivity

Diels–Alder reactions, as concerted cycloadditions, are stereospecific. Stereochemical information of the diene and the
dienophile are retained in the product, as a syn addition with respect to each component. For example, substituents in a cis
(trans, resp.) relationship on the double bond of the dienophile give rise to substituents that are cis (trans, resp.) on those
same carbons with respect to the cyclohexene ring. Likewise, cis,cis- and trans,trans-disubstituted dienes give cis
substituents at these carbons of the product whereas cis,trans-disubstituted dienes give trans substituents:[19][20]

Diels–Alder reactions in which adjacent stereocenters are generated at the two ends of the newly formed single bonds
imply two different possible stereochemical outcomes. This is a stereoselective situation based on the relative orientation
of the two separate components when they react with each other. In the context of the Diels–Alder reaction, the transition
state in which the most significant substituent (an electron-withdrawing and/or conjugating group) on the dienophile is
oriented towards the diene π system and slips under it as the reaction
takes place is known as the endo transition state. In the alternative exo
transition state, it is oriented away from it. (There is a more general
usage of the terms endo and exo in stereochemical nomenclature.)

In cases where the dienophile has a single electron-withdrawing /

conjugating substituent, or two electron-withdrawing / conjugating
substituents cis to each other, the outcome can often be predicted. In
these "normal demand" Diels–Alder scenarios, the endo transition state Endo and exo transition states for
is typically preferred, despite often being more sterically congested. cyclopentadiene adding to acrolein; endo/exo
This preference is known as the Alder endo rule. As originally stated product ratio for this and various other dienophiles
by Alder, the transition state that is preferred is the one with a
"maximum accumulation of double bonds." Endo selectivity is
typically higher for rigid dienophiles such as maleic anhydride and benzoquinone; for others, such as acrylates and
crotonates, selectivity is not very pronounced.[21]

The most widely accepted explanation for the origin of this effect is a favorable interaction between the π systems of the
dienophile and the diene, an interaction described as a secondary orbital effect, though dipolar and van der Waals
attractions may play a part as well, and solvent can sometimes make a substantial difference in selectivity.[6][22][23] The
secondary orbital overlap explanation was first proposed by Woodward and Hoffmann.[24] In this explanation, the orbitals
associated with the group in conjugation with the dienophile double-bond overlap with the interior orbitals of the diene, a
situation that is possible only for the endo transition state. Although the original explanation only invoked the orbital on
the atom α to the dienophile double bond, Salem and Houk have subsequently proposed that orbitals on the α and β
carbons both participate when molecular geometry allows.[25]

Often, as with highly substituted dienes, very bulky dienophiles, or reversible reactions (as in the case of furan as diene),
steric effects can override the normal endo selectivity in favor of the exo isomer.

The diene
The diene component of the Diels–Alder reaction can be either open-chain or cyclic, and it can host many different types
of substituents.[6] It must, however, be able to exist in the s-cis conformation, since this is the only conformer that can
participate in the reaction. Though butadienes are typically more stable in the s-trans conformation, for most cases energy
difference is small (~2–5 kcal/mol).[26]

A bulky substituent at the C2 or C3 position can increase reaction rate by destabilizing the s-trans conformation and
forcing the diene into the reactive s-cis conformation. 2-tert-butyl-buta-1,3-diene, for example, is 27 times more reactive
than simple butadiene.[6][27] Conversely, a diene having bulky substituents at both C2 and C3 is less reactive because the
steric interactions between the substituents destabilize the s-cis conformation.[27]

Dienes with bulky terminal substituents (C1 and C4) decrease the rate of reaction, presumably by impeding the approach
of the diene and dienophile.[28]
An especially reactive diene is 1-methoxy-3-trimethylsiloxy-buta-1,3-diene, otherwise known as Danishefsky's diene.[29] It
has particular synthetic utility as means of furnishing α,β–unsaturated cyclohexenone systems by elimination of the 1-
methoxy substituent after deprotection of the enol silyl ether. Other synthetically useful derivatives of Danishefsky's diene
include 1,3-alkoxy-1-trimethylsiloxy-1,3-butadienes (Brassard dienes)[30] and 1-dialkylamino-3-trimethylsiloxy-1,3-
butadienes (Rawal dienes).[31] The increased reactivity of these and similar dienes is a result of synergistic contributions
from donor groups at C1 and C3, raising the HOMO significantly above that of a comparable monosubstituted diene.[3]

Unstable (and thus highly reactive) dienes can be synthetically useful, e.g. o-quinodimethanes can be generated in situ. In
contrast, stable dienes, such as naphthalene, require forcing conditions and/or highly reactive dienophiles, such as N-
phenylmaleimide. Anthracene, being less aromatic (and therefore more reactive for Diels–Alder syntheses) in its central
ring can form a 9,10 adduct with maleic anhydride at 80 °C and even with acetylene, a weak dienophile, at 250 °C.[32]

The dienophile
In a normal demand Diels–Alder reaction, the dienophile has an electron-withdrawing group in conjugation with the
alkene; in an inverse-demand scenario, the dienophile is conjugated with an electron-donating group.[9] Dienophiles can be
chosen to contain a "masked functionality". The dienophile undergoes Diels–Alder reaction with a diene introducing such
a functionality onto the product molecule. A series of reactions then follow to transform the functionality into a desirable
group. The end product cannot be made in a single DA step because equivalent dienophile is either unreactive or
inaccessible. An example of such approach is the use of α-chloroacrylonitrile (CH2=CClCN). When reacted with a diene,
this dienophile will introduce α-chloronitrile functionality onto the product molecule. This is a "masked functionality"
which can be then hydrolyzed to form a ketone. α-Chloroacrylonitrile dienophile is an equivalent of ketene dienophile
(CH2=C=O), which would produce same product in one DA step. The problem is that ketene itself cannot be used in
Diels–Alder reactions because it reacts with dienes in unwanted manner (by [2+2] cycloaddition), and therefore "masked
functionality" approach has to be used.[33] Other such functionalities are phosphonium substituents (yielding exocyclic
double bonds after Wittig reaction), various sulfoxide and sulfonyl functionalities (both are acetylene equivalents), and
nitro groups (ketene equivalents).[6]

Variants on the classical Diels–Alder reaction

Hetero-Diels–Alder
Diels–Alder reactions involving at least one heteroatom are also known and are collectively called hetero-Diels–Alder
reactions.[34] Carbonyl groups, for example, can successfully react with dienes to yield dihydropyran rings, a reaction
known as the oxo-Diels–Alder reaction, and imines can be used, either as the dienophile or at various sites in the diene, to
form various N-heterocyclic compounds through the aza-Diels–Alder reaction. Nitroso compounds (R-N=O) can react
with dienes to form oxazines. Chlorosulfonyl isocyanate can be utilized as a dienophile to prepare Vince lactam.[6][35]

Lewis acid activation

Lewis acids, such as zinc chloride, boron trifluoride, tin tetrachloride, or aluminium chloride, can catalyze Diels–Alder
reactions by binding to the dienophile. Traditionally, the enhanced Diels-Alder reactivity is ascribed to the ability of the
Lewis acid to lower the LUMO of the activated dienophile, which results in a smaller normal electron demand HOMO-
LUMO orbital energy gap and hence more stabilizing orbital interactions.[36][37][38]
Recent studies, however, have shown that this rationale behind Lewis acid-catalyzed Diels–Alder reactions is
incorrect.[39][40][41][42] It is found that Lewis acids accelerate the Diels–Alder reaction by reducing the destabilizing steric
Pauli repulsion between the interacting diene and dienophile and not by lowering the energy of the dienophile's LUMO and
consequently, enhancing the normal electron demand orbital interaction. The Lewis acid binds via a donor-acceptor
interaction to the dienophile and via that mechanism polarizes occupied orbital density away from the reactive C=C double
bond of the dienophile towards the Lewis acid. This reduced occupied orbital density on C=C double bond of the
dienophile will, in turn, engage in a less repulsive closed-shell-closed-shell orbital interaction with the incoming diene,
reducing the destabilizing steric Pauli repulsion and hence lowers the Diels–Alder reaction barrier. In addition, the Lewis
acid catalyst also increases the asynchronicity of the Diels–Alder reaction, making the occupied π-orbital located on the
C=C double bond of the dienophile asymmetric. As a result, this enhanced asynchronicity leads to an extra reduction of the
destabilizing steric Pauli repulsion as well as a diminishing pressure on the reactants to deform, in other words, it reduced
the destabilizing activation strain (also known as distortion energy).[43] This working catalytic mechanism is known as
Pauli-lowering catalysis,[44] which is operative in a variety of organic reactions.[45][46][47]

The original rationale behind Lewis acid-catalyzed Diels–Alder reactions is incorrect,[39][48][49][50] because besides
lowering the energy of the dienophile's LUMO, the Lewis acid also lowers the energy of the HOMO of the dienophile and
hence increases the inverse electron demand LUMO-HOMO orbital energy gap. Thus, indeed Lewis acid catalysts
strengthen the normal electron demand orbital interaction by lowering the LUMO of the dienophile, but, they
simultaneously weaken the inverse electron demand orbital interaction by also lowering the energy of the dienophile's
HOMO. These two counteracting phenomena effectively cancel each other, resulting in nearly unchanged orbital
interactions when compared to the corresponding uncatalyzed Diels–Alder reactions and making this not the active
mechanism behind Lewis acid-catalyzed Diels–Alder reactions.

Asymmetric Diels–Alder
Many methods have been developed for influencing the stereoselectivity of the Diels–Alder reaction, such as the use of
chiral auxiliaries, catalysis by chiral Lewis acids,[51] and small organic molecule catalysts.[6] Evans' oxazolidinones,[52]
oxazaborolidines,[53][54][55] bis-oxazoline–copper chelates,[56] imidazoline catalysis,[57] and many other methodologies
exist for effecting diastereo- and enantioselective Diels–Alder reactions.

Hexadehydro Diels–Alder
In the hexadehydro Diels–Alder reaction, alkynes and diynes are used instead of alkenes and dienes, forming an unstable
benzyne intermediate which can then be trapped to form an aromatic product. This reaction allows the formation of heavily
functionalized aromatic rings in a single step.[58][59]

Applications and natural occurrence

Asymmetric Diels-Alder reaction is

one step in the biosynthesis of the
statin lovastatin.[60]

The retro-Diels–Alder reaction is used in the industrial production of cyclopentadiene. Cyclopentadiene is a precursor to
various norbornenes, which are common monomers. The Diels–Alder reaction is also employed in the production of
vitamin B6.
 Typical route for production of ethylidene norbornene
from cyclopentadiene through vinyl norbornene.[61]

History
The Diels-Alder reaction was the culmination
of several intertwined research threads, some
near misses, and ultimately, the insightful
recognition of a general principle by Otto Diels
and Kurt Alder. Their seminal work, detailed in
a series of 28 articles published in the Justus
Liebigs Annalen der Chemie and Berichte der The reaction discovered by Diels and Alder in 1928.

deutschen chemischen Gesellschaft from 1928

to 1937, established the reaction's wide applicability and its importance in constructing six-membered rings. The first 19
articles were authored by Diels and Alder, while the later articles were authored by Diels and various other
coauthors.[62][63] However, the history of the reaction extends further back, revealing a fascinating narrative of discoveries
missed and opportunities overlooked.[64]

Several chemists, working independently in the late 19th and early 20th centuries, encountered reactions that, in retrospect,
involved the Diels-Alder process but remained unrecognized as such.[64]

Theodor Zincke performed a series of experiments between 1892 and 1912 involving
tetrachlorocyclopentadienone, a highly reactive diene analogue.[65][66][67][68]
In 1910, Sergey Lebedev systematically investigated thermal polymerization of three conjugated dienes
(butadiene, isoprene and dimethylbutadiene), a process now recognized as a Diels-Alder self-reaction,
providing a detailed analysis of the dimerization products and recognizing the importance of the conjugated
system in the process.[69] Five years earlier, Carl Harries studied the degradation of natural rubber, leading
him to propose a cyclic structure for the polymer.[70]
Hermann Staudinger's work with ketenes published in 1912 covered both [2+2] cycloadditions, where one
molecule of a ketene reacted with an unsaturated compound to form a four-membered ring, and,
importantly, [4+2] cycloadditions. In the latter case, two molecules of ketene combined with one molecule of
an unsaturated compound (such as a quinone) to yield a six-membered ring.[71] While not a classic Diels-
Alder reaction in the typical sense of a conjugated diene and a separate dienophile, Staudinger's
observation of this [4+2] process, forming a six-membered ring, foreshadowed the later work of Diels and
Alder. However, his focus remained primarily on the more common [2+2] ketene cycloaddition.
Hans von Euler-Chelpin and K. O. Josephson, investigating isoprene and butadiene reactions in 1920, both
observed products consistent with Diels-Alder cycloadditions, but didn't go on to research it further.[72]
Perhaps the most striking near miss came from Walter Albrecht in early 1900s. Working in Johannes
Thiele's laboratory, Albrecht investigated the reaction of cyclopentadiene with para-benzoquinone. His 1902
doctoral dissertation clearly describes the formation of the Diels-Alder adduct, even providing (incorrect)
structural assignments.[73] However, influenced by Thiele's focus on conjugation and partial valence,
Albrecht in his 1906 publication[74] interpreted the reaction as a 1,4-addition followed by a 1,2-addition,
completely overlooking the cycloaddition aspect.
While these observations hinted at the possibility of a broader class of cycloaddition reactions, they remained isolated
incidents, their significance not fully appreciated at the time, with none of the researchers even trying to generalize their
findings.[64]

It fell to Diels and Alder to synthesize these disparate threads into a coherent whole. Unlike the earlier researchers, they
recognized the generality and predictability of the diene and dienophile combining to form a cyclic structure. Through their
systematic investigations, exploring various combinations of dienes and dienophiles, they firmly established the "diene
synthesis" as a powerful new synthetic method. Their meticulous work not only demonstrated the reaction's scope and
versatility but also laid the groundwork for future theoretical developments, including the Woodward-Hoffmann rules,
which would provide a deeper understanding of pericyclic reactions, including the Diels-Alder.

Applications in total synthesis

The Diels–Alder reaction was one step in an early preparation of the steroids cortisone and cholesterol.[75] The reaction
involved the addition of butadiene to a quinone.

Diels–Alder reactions were used in the original synthesis of prostaglandins F2α and E2.[76] The Diels–Alder reaction
establishes the relative stereochemistry of three contiguous stereocenters on the prostaglandin cyclopentane core.
Activation by Lewis acidic cupric tetrafluoroborate was required.

A Diels–Alder reaction was used in the synthesis of disodium prephenate,[77] a biosynthetic precursor of the amino acids
phenylalanine and tyrosine.

A synthesis of reserpine uses a Diels–Alder reaction to set the cis-decalin framework of the D and E rings.[78]

In another synthesis of reserpine, the cis-fused D and E rings was formed by a Diels–Alder reaction. Intramolecular Diels–
Alder of the pyranone below with subsequent extrusion of carbon dioxide via a retro [4+2] afforded the bicyclic lactam.
Epoxidation from the less hindered α-face, followed by epoxide opening at the less hindered C18 afforded the desired
stereochemistry at these positions, while the cis-fusion was achieved with hydrogenation, again proceeding primarily from
the less hindered face.[79]

A pyranone was similarly used as the dienophile in the total synthesis of taxol.[80] The intermolecular reaction of the
hydroxy-pyrone and α,β–unsaturated ester shown below suffered from poor yield and regioselectivity; however, when
directed by phenylboronic acid[81] the desired adduct could be obtained in 61% yield after cleavage of the boronate with
neopentyl glycol. The stereospecificity of the Diels–Alder reaction in this instance allowed for the definition of four
stereocenters that were carried on to the final product.
A Diels–Alder reaction is a key step in the synthesis of (-)-furaquinocin C.[82]

Tabersonine was prepared by a Diels–Alder reaction to establish cis relative stereochemistry of the alkaloid core.
Conversion of the cis-aldehyde to its corresponding alkene by Wittig olefination and subsequent ring-closing metathesis
with a Schrock catalyst gave the second ring of the alkaloid core. The diene in this instance is notable as an example of a
1-amino-3-siloxybutadiene, otherwise known as a Rawal diene.[83]

(+)-Sterpurene can be prepared by asymmetric D-A reaction[84] that featured a remarkable intramolecular Diels–Alder
reaction of an allene. The [2,3]-sigmatropic rearrangement of the thiophenyl group to give the sulfoxide as below
proceeded enantiospecifically due to the predefined stereochemistry of the propargylic alcohol. In this way, the single
allene isomer formed could direct the Diels–Alder reaction to occur on only one face of the generated 'diene'.

The tetracyclic core of the antibiotic (-)-tetracycline was prepared with a Diels–Alder reaction. Thermally initiated,
conrotatory opening of the benzocyclobutene generated the o-quinodimethane, which reacted intermolecularly to give the
tetracycline skeleton. The dienophile's free hydroxyl group is integral to the success of the reaction, as hydroxyl-protected
variants did not react under several different reaction conditions.[85]
Takemura et al. synthesized cantharidin in 1980 by Diels–Alder reaction, utilizing high pressure.[86]

Synthetic applications of the Diels–Alder reaction have been reviewed extensively.[87][88][89][90][91]

See also
Bradsher cycloaddition
Wagner-Jauregg reaction
Aza-Diels–Alder reaction

References
1. Kloetzel, M. C. (1948). "The Diels–Alder Reaction with Maleic Anhydride". Organic Reactions. Vol. 4. pp. 1–
59. doi:10.1002/0471264180.or004.01 ([Link] ISBN 978-
0471264187.
2. Holmes, H. L. (1948). "The Diels-Alder Reaction Ethylenic and Acetylenic Dienophiles". Organic Reactions.
Vol. 4. pp. 60–173. doi:10.1002/0471264180.or004.02 ([Link]
ISBN 978-0471264187.
3. Nicolaou, K. C.; Snyder, S. A.; Montagnon, T.; Vassilikogiannakis, G. (2002). "The Diels-Alder Reaction in
Total Synthesis". Angewandte Chemie International Edition. 41 (10): 1668–1698. doi:10.1002/1521-
3773(20020517)41:10<1668::AID-ANIE1668>[Link];2-Z ([Link]
517%2941%3A10%3C1668%3A%3AAID-ANIE1668%[Link]%3B2-Z). PMID 19750686 ([Link]
[Link]/19750686).
4. Atilla Tasdelen, Mehmet (2011). "Diels–Alder "click" reactions: recent applications in polymer and material
science". Polymer Chemistry. 2 (10): 2133–2145. doi:10.1039/C1PY00041A ([Link]
PY00041A).
5. Zweifel, G. S.; Nantz, M. H. (2007). Modern Organic Synthesis: An Introduction. W. H. Freeman and Co.
ISBN 978-0-7167-7266-8.
6. Carey, Part B., pp. 474–526
7. Dewar, M. J.; Olivella, S.; Stewart, J. J. (1986). "Mechanism of the Diels-Alder reaction: Reactions of
butadiene with ethylene and cyanoethylenes". Journal of the American Chemical Society. 108 (19): 5771–
5779. doi:10.1021/ja00279a018 ([Link] PMID 22175326 ([Link]
[Link]/22175326).
8. Carey, Part A., pp. 836–50
9. Carey, Part A., p. 839
10. Gajewski, J. J.; Peterson, K. B.; Kagel, J. R. (1987). "Transition-state structure variation in the Diels–Alder
reaction from secondary deuterium kinetic isotope effects: The reaction of a nearly symmetrical diene and
dienophile is nearly synchronous". Journal of the American Chemical Society. 109 (18): 5545–5546.
doi:10.1021/ja00252a052 ([Link]
11. Houk, K. N.; Lin, Y. T.; Brown, F. K. (1986). "Evidence for the concerted mechanism of the Diels–Alder
reaction of butadiene with ethylene". Journal of the American Chemical Society. 108 (3): 554–556.
doi:10.1021/ja00263a059 ([Link] PMID 22175504 ([Link]
[Link]/22175504).
12. Goldstein, E.; Beno, B.; Houk, K. N. (1996). "Density Functional Theory Prediction of the Relative Energies
and Isotope Effects for the Concerted and Stepwise Mechanisms of the Diels−Alder Reaction of Butadiene
and Ethylene". Journal of the American Chemical Society. 118 (25): 6036–6043. doi:10.1021/ja9601494 (htt
ps://[Link]/10.1021%2Fja9601494).
13. Breslow, R.; Guo, T. (1988). "Diels-Alder reactions in nonaqueous polar solvents. Kinetic effects of
chaotropic and antichaotropic agents and of β-cyclodextrin". Journal of the American Chemical Society. 110
(17): 5613–5617. doi:10.1021/ja00225a003 ([Link]
14. Rideout, D. C.; Breslow, R. (1980). "Hydrophobic acceleration of Diels-Alder reactions". Journal of the
American Chemical Society. 102 (26): 7816–7817. doi:10.1021/ja00546a048 ([Link]
00546a048).
15. Breslow, R.; Rizzo, C. J. (1991). "Chaotropic salt effects in a hydrophobically accelerated Diels–Alder
reaction". Journal of the American Chemical Society. 113 (11): 4340–4341. doi:10.1021/ja00011a052 (http
s://[Link]/10.1021%2Fja00011a052).
16. Blokzijl, Wilfried; Engberts, Jan B. F. N. (1992). "Initial-State and Transition-State Effects on Diels–Alder
Reactions in Water and Mixed Aqueous Solvents". Journal of the American Chemical Society. 114 (13):
5440–5442. doi:10.1021/ja00039a074 ([Link]
17. Ashby, E. C.; Chao, L.-C.; Neumann, H. M. (1973). "Organometallic reaction mechanisms. XII. Mechanism
of methylmagnesium bromide addition to benzonitrile". Journal of the American Chemical Society. 95 (15):
4896–4904. doi:10.1021/ja00796a022 ([Link]
18. Fleming, I. (1990). Frontier Orbital and Organic Chemical Reactions. Chichester, UK: Wiley. ISBN 978-
0471018193.
19. Kirmse, W.; Mönch, D. (1991). "Umlagerungen von 1,4,4- und 2,2,5-Trimethylbicyclo[3.2.1]oct-6-yl-
Kationen". Chemische Berichte. 124 (1): 237–240. doi:10.1002/cber.19911240136 ([Link]
2%2Fcber.19911240136).
20. Bérubé, G.; DesLongchamps, P. (1987). "Stéréosélection acyclique-1,5: Synthèse de la chaîne latérale
optiquement active de la vitamine E". Bulletin de la Société Chimique de France. 1: 103–115.
21. Houk, K. N.; Luskus, L. J. (1971). "Influence of steric interactions on endo stereoselectivity". Journal of the
American Chemical Society. 93 (18): 4606–4607. doi:10.1021/ja00747a052 ([Link]
0747a052).
22. Kobuke, Y.; Sugimoto, T.; Furukawa, J.; Fueno, T. (1972). "Role of attractive interactions in endo–exo
stereoselectivities of Diels–Alder reactions". Journal of the American Chemical Society. 94 (10): 3633–3635.
doi:10.1021/ja00765a066 ([Link]
23. Williamson, K. L.; Hsu, Y.-F. L. (1970). "Stereochemistry of the Diels–Alder reaction. II. Lewis acid catalysis
of syn-anti isomerism". Journal of the American Chemical Society. 92 (25): 7385–7389.
doi:10.1021/ja00728a022 ([Link]
24. Woodward, R. B.; Hoffmann, R. (22 October 2013). The conservation of orbital symmetry. Weinheim.
ISBN 9781483282046. OCLC 915343522 ([Link]
25. Wannere, Chaitanya S.; Paul, Ankan; Herges, Rainer; Houk, K. N.; Schaefer, Henry F.; Schleyer, Paul Von
Ragué (2007). "The existence of secondary orbital interactions". Journal of Computational Chemistry. 28
(1): 344–361. doi:10.1002/jcc.20532 ([Link] ISSN 1096-987X ([Link]
[Link]/issn/1096-987X). PMID 17109435 ([Link]
S2CID 26096085 ([Link]
26. Carey, Part A, p. 149
27. Backer, H. J. (1939). "Le 2,3-Ditertiobutylbutadiène". Recueil des Travaux Chimiques des Pays-Bas. 58 (7):
643–661. doi:10.1002/recl.19390580712 ([Link]
28. Craig, D.; Shipman, J. J.; Fowler, R. B. (1961). "The Rate of Reaction of Maleic Anhydride with 1,3-Dienes
as Related to Diene Conformation". Journal of the American Chemical Society. 83 (13): 2885–2891.
doi:10.1021/ja01474a023 ([Link]
29. Danishefsky, S.; Kitahara, T. (1974). "Useful diene for the Diels–Alder reaction". Journal of the American
Chemical Society. 96 (25): 7807–7808. doi:10.1021/ja00832a031 ([Link]
1).
30. Savard, J.; Brassard, P. (1979). "Regiospecific syntheses of quinones using vinylketene acetals derived
from unsaturated esters". Tetrahedron Letters. 20 (51): 4911–4914. doi:10.1016/S0040-4039(01)86747-2 (h
ttps://[Link]/10.1016%2FS0040-4039%2801%2986747-2).
31. Kozmin, S. A.; Rawal, V. H. (1997). "Preparation and Diels−Alder Reactivity of 1-Amino-3-siloxy-1,3-
butadienes". Journal of Organic Chemistry. 62 (16): 5252–5253. doi:10.1021/jo970438q ([Link]
021%2Fjo970438q).
32. Margareta Avram (1983). Chimie organica p. 318-323. Editura Academiei Republicii Socialiste România
33. Ranganathan, S.; Ranganathan, D.; Mehrotra, A. K. (1977). "Ketene Equivalents". Synthesis. 1977 (5):
289–296. doi:10.1055/s-1977-24362 ([Link] S2CID 260335918 (https://
[Link]/CorpusID:260335918).
34. Roush, W. R. (1991). "Intramolecular Diels–Alder Reactions". In Trost, B. M.; Flemming, I. (eds.).
Comprehensive Organic Synthesis. Vol. 5. pp. 513–550. doi:10.1016/B978-0-08-052349-1.00131-1 (https://
[Link]/10.1016%2FB978-0-08-052349-1.00131-1). ISBN 978-0-08-052349-1.
35. Grieco, P. A.; Larsen, S. D. (1990). "Iminium Ion-Based Diels–Alder Reactions: N-Benzyl-2-Azanorborene"
([Link] (PDF). Organic Syntheses. 68: 206.
doi:10.15227/orgsyn.068.0206 ([Link]
36. Houk, Kendall N. (1 November 1975). "Frontier molecular orbital theory of cycloaddition reactions" ([Link]
[Link]/10.1021/ar50095a001). Accounts of Chemical Research. 8 (11): 361–369. doi:10.1021/ar50095a001
([Link] ISSN 0001-4842 ([Link]
37. Fleming, Ian (2009). Molecular orbitals and organic chemical reactions. Chichester, West Sussex, U.K.:
Wiley. ISBN 9780470746592.
38. Clayden, Jonathan (2012). Organic chemistry (2nd ed.). Oxford: Oxford University Press.
ISBN 9780199270293.
39. Vermeeren, Pascal; Hamlin, Trevor A.; Fernández, Israel; Bickelhaupt, F. Matthias (6 April 2020). "How
Lewis Acids Catalyze Diels–Alder Reactions" ([Link]
Angewandte Chemie International Edition. 59 (15): 6201–6206. doi:10.1002/anie.201914582 ([Link]
g/10.1002%2Fanie.201914582). PMC 7187354 ([Link]
PMID 31944503 ([Link]
40. Vermeeren, Pascal; Hamlin, Trevor A.; Fernández, Israel; Bickelhaupt, F. Matthias (2020). "Origin of rate
enhancement and asynchronicity in iminium catalyzed Diels–Alder reactions" ([Link]
pmc/articles/PMC8163289). Chemical Science. 11 (31): 8105–8112. doi:10.1039/D0SC02901G ([Link]
org/10.1039%2FD0SC02901G). PMC 8163289 ([Link]
PMID 34094173 ([Link]
41. Vermeeren, Pascal; Hamlin, Trevor A.; Bickelhaupt, F. Matthias; Fernández, Israel (17 March 2021).
"Bifunctional Hydrogen Bond Donor-Catalyzed Diels–Alder Reactions: Origin of Stereoselectivity and Rate
Enhancement" ([Link] Chemistry: A European Journal.
27 (16): 5180–5190. doi:10.1002/chem.202004496 ([Link]
PMC 8049058 ([Link] PMID 33169912 ([Link]
[Link]/33169912).
42. Vermeeren, Pascal; Tiezza, Marco Dalla; Dongen, Michelle; Fernández, Israel; Bickelhaupt, F. Matthias;
Hamlin, Trevor A. (21 July 2021). "Lewis Acid-Catalyzed Diels-Alder Reactions: Reactivity Trends across the
Periodic Table" ([Link] Chemistry: A European Journal.
27 (41): 10610–10620. doi:10.1002/chem.202100522 ([Link]
PMC 8360170 ([Link] PMID 33780068 ([Link]
[Link]/33780068).
43. Vermeeren, Pascal; Hamlin, Trevor A.; Bickelhaupt, F. Matthias (2021). "Origin of asynchronicity in Diels–
Alder reactions" ([Link] Physical Chemistry Chemical
Physics. 23 (36): 20095–20106. Bibcode:2021PCCP...2320095V ([Link]
CCP...2320095V). doi:10.1039/D1CP02456F ([Link] PMC 8457343 (htt
ps://[Link]/pmc/articles/PMC8457343). PMID 34499069 ([Link]
499069).
44. Hamlin, Trevor A.; Bickelhaupt, F. Matthias; Fernández, Israel (20 April 2021). "The Pauli Repulsion-
Lowering Concept in Catalysis" ([Link]
i_RepulsionLowering_Concept_in_Catalysis.pdf) (PDF). Accounts of Chemical Research. 54 (8): 1972–
1981. doi:10.1021/[Link].1c00016 ([Link]
hdl:1871.1/a0090b38-9ab8-4c32-9d9a-b3d5de4e5ed3 ([Link]
32-9d9a-b3d5de4e5ed3). ISSN 0001-4842 ([Link] PMID 33759502 (h
ttps://[Link]/33759502). S2CID 232337915 ([Link]
2337915).
45. Vermeeren, Pascal; Brinkhuis, Francine; Hamlin, Trevor A.; Bickelhaupt, F. Matthias (April 2020). "How
Alkali Cations Catalyze Aromatic Diels-Alder Reactions" ([Link]
7256). Chemistry: An Asian Journal. 15 (7): 1167–1174. doi:10.1002/asia.202000009 ([Link]
2%2Fasia.202000009). PMC 7187256 ([Link]
PMID 32012430 ([Link]
46. Hansen, Thomas; Vermeeren, Pascal; Yoshisada, Ryoji; Filippov, Dmitri V.; van der Marel, Gijsbert A.;
Codée, Jeroen D. C.; Hamlin, Trevor A. (19 February 2021). "How Lewis Acids Catalyze Ring-Openings of
Cyclohexene Oxide" ([Link] The Journal of Organic
Chemistry. 86 (4): 3565–3573. doi:10.1021/[Link].0c02955 ([Link]
PMC 7901664 ([Link] PMID 33538169 ([Link]
[Link]/33538169).
47. Tiekink, Eveline H.; Vermeeren, Pascal; Bickelhaupt, F. Matthias; Hamlin, Trevor A. (7 October 2021). "How
Lewis Acids Catalyze Ene Reactions". European Journal of Organic Chemistry. 2021 (37): 5275–5283.
doi:10.1002/ejoc.202101107 ([Link] hdl:2066/241097 ([Link]
[Link]/2066%2F241097). S2CID 239089361 ([Link]
48. Vermeeren, Pascal; Hamlin, Trevor A.; Fernández, Israel; Bickelhaupt, F. Matthias (2020). "Origin of rate
enhancement and asynchronicity in iminium catalyzed Diels–Alder reactions" ([Link]
pmc/articles/PMC8163289). Chemical Science. 11 (31): 8105–8112. doi:10.1039/D0SC02901G ([Link]
org/10.1039%2FD0SC02901G). PMC 8163289 ([Link]
PMID 34094173 ([Link]
49. Vermeeren, Pascal; Hamlin, Trevor A.; Bickelhaupt, F. Matthias; Fernández, Israel (17 March 2021).
"Bifunctional Hydrogen Bond Donor-Catalyzed Diels–Alder Reactions: Origin of Stereoselectivity and Rate
Enhancement" ([Link] Chemistry: A European Journal.
27 (16): 5180–5190. doi:10.1002/chem.202004496 ([Link]
PMC 8049058 ([Link] PMID 33169912 ([Link]
[Link]/33169912).
50. Vermeeren, Pascal; Tiezza, Marco Dalla; Dongen, Michelle; Fernández, Israel; Bickelhaupt, F. Matthias;
Hamlin, Trevor A. (21 July 2021). "Lewis Acid-Catalyzed Diels-Alder Reactions: Reactivity Trends across the
Periodic Table" ([Link] Chemistry: A European Journal.
27 (41): 10610–10620. doi:10.1002/chem.202100522 ([Link]
PMC 8360170 ([Link] PMID 33780068 ([Link]
[Link]/33780068).
51. White, James D.; Shaw, Subrata (2011). "cis-2,5-Diaminobicyclo[2.2.2]octane, a New Scaffold for
Asymmetric Catalysis via Salen−Metal Complexes". Org. Lett. 13 (9): 2488–91. doi:10.1021/ol2007378 (http
s://[Link]/10.1021%2Fol2007378). PMID 21462988 ([Link]
52. Evans, D. A.; Chapman, K. T.; Bisaha, J. (1988). "Asymmetric Diels–Alder cycloaddition reactions with chiral
α,β-unsaturated N-acyloxazolidinones". Journal of the American Chemical Society. 110 (4): 1238–1256.
doi:10.1021/ja00212a037 ([Link]
53. Corey, E. J.; Loh, T. P. (1991). "First application of attractive intramolecular interactions to the design of
chiral catalysts for highly enantioselective Diels–Alder reactions". Journal of the American Chemical
Society. 113 (23): 8966–8967. doi:10.1021/ja00023a066 ([Link]
54. Corey, E. J.; Shibata, T.; Lee, T. W. (2002). "Asymmetric Diels-Alder reactions catalyzed by a triflic acid
activated chiral oxazaborolidine". Journal of the American Chemical Society. 124 (15): 3808–3809.
doi:10.1021/ja025848x ([Link] PMID 11942799 ([Link]
[Link]/11942799).
55. Ryu, D. H.; Corey, E. J. (2003). "Triflimide activation of a chiral oxazaborolidine leads to a more general
catalytic system for enantioselective Diels-Alder addition". Journal of the American Chemical Society. 125
(21): 6388–6390. doi:10.1021/ja035393r ([Link] PMID 12785777 ([Link]
[Link]/12785777).
56. Johnson, J. S.; Evans, D. A. (2000). "Chiral bis(oxazoline) copper(II) complexes: Versatile catalysts for
enantioselective cycloaddition, Aldol, Michael, and carbonyl Ene reactions". Accounts of Chemical
Research. 33 (6): 325–335. doi:10.1021/ar960062n ([Link]
PMID 10891050 ([Link]
57. Ahrendt, K. A.; Borths, C. J.; MacMillan, D. W. C. (2000). "New Strategies for Organic Catalysis: The First
Highly Enantioselective Organocatalytic Diels−Alder Reaction". Journal of the American Chemical Society.
122 (17): 4243–4244. doi:10.1021/ja000092s ([Link]
58. Hoye, T. R.; Baire, B.; Niu, D.; Willoughby, P. H.; Woods, B. P. (2012). "The hexadehydro-Diels–Alder
reaction" ([Link] Nature. 490 (7419): 208–212.
doi:10.1038/nature11518 ([Link] PMC 3538845 ([Link]
[Link]/pmc/articles/PMC3538845). PMID 23060191 ([Link]
59. Fluegel, Lucas L.; Hoye, Thomas R. (2021). "Hexadehydro-Diels–Alder Reaction: Benzyne Generation via
Cycloisomerization of Tethered Triynes" ([Link] Chem.
Rev. 121 (4): 2413–2444. doi:10.1021/[Link].0c00825 ([Link]
825). PMC 8008985 ([Link] PMID 33492939 ([Link]
[Link]/33492939).
60. Minami, Atsushi; Oikawa, Hideaki (2016). "Recent advances of Diels–Alderases involved in natural product
biosynthesis" ([Link] The Journal of Antibiotics. 69 (7): 500–506.
doi:10.1038/ja.2016.67 ([Link] PMID 27301662 ([Link]
[Link]/27301662). S2CID 30482282 ([Link]
61. Behr, Arno (2000). "Organometallic Compounds and Homogeneous Catalysis". Ullmann's Encyclopedia of
Industrial Chemistry. doi:10.1002/14356007.a18_215 ([Link]
ISBN 978-3527306732.
62. * Diels, O.; Alder, K. (1928). "Synthesen in der hydroaromatischen Reihe, I. Mitteilung: Anlagerungen von
"Di-en"-kohlenwasserstoffen". Justus Liebigs Annalen der Chemie. 460: 98–122.
doi:10.1002/jlac.19284600106 ([Link]
Diels, O.; Alder, K. (1929). "Synthesen in der hydroaromatischen Reihe, II. Mitteilung: Über Cantharidin".
Berichte der Deutschen Chemischen Gesellschaft. 62 (3): 554–562. doi:10.1002/cber.19290620318 (htt
ps://[Link]/10.1002%2Fcber.19290620318).
Diels, O.; Alder, K. (1929). "Synthesen in der hydroaromatischen Reihe, III. Mitteilung: Synthese von
Terpenen, Camphern, hydroaromatischen und heterocyclischen Systemen. Mitbearbeitet von den
Herren Wolfgang Lübbert, Erich Naujoks, Franz Querberitz, Karl Röhl, Harro Segeberg". Justus Liebigs
Annalen der Chemie. 470: 62–103. doi:10.1002/jlac.19294700106 ([Link]
4700106).
Diels, O.; Alder, K. (1929). "Synthesen in der hydroaromatischen Reihe, IV. Mitteilung: Über die
Anlagerung von Maleinsäure-anhydrid an arylierte Diene, Triene und Fulvene (Mitbearbeitet von Paul
Pries)". Berichte der Deutschen Chemischen Gesellschaft. 62 (8): 2081–2087.
doi:10.1002/cber.19290620829 ([Link]
Diels, O.; Alder, K. (1929). "Synthesen in der hydroaromatischen Reihe, V. Über Δ4-Tetrahydro-o-
phthalsäure (Stellungnahme zu der Mitteilung von E. H. Farmer und F. L. Warren: Eigenschaften
konjugierter Doppelbindungen (VII)". Berichte der Deutschen Chemischen Gesellschaft. 62 (8): 2087–
2090. doi:10.1002/cber.19290620830 ([Link]
Diels, O.; Alder, K. (1929). "Synthesen in der hydroaromatischen Reihe, VI. Mitteilung, Kurt Alder und
Gerhard Stein: Über partiell hydrierte Naphtho- und Anthrachinone mit Wasserstoff in γ- bzw. δ-Stellung.
(Mitbearbeitet von Paul Pries und Hans Winckler)". Berichte der Deutschen Chemischen Gesellschaft.
62 (8): 2337–2372. doi:10.1002/cber.19290620872 ([Link]
Diels, O.; Alder, K. (1930). "Synthesen in der hydroaromatischen Reihe, VII. Mitteilung. (Mitbearbeitet
von den Harren Ernst Petersen und Franz Querberitz.)". Justus Liebigs Annalen der Chemie. 478: 137–
154. doi:10.1002/jlac.19304780109 ([Link]
Diels, O.; Alder, K. (1931). "Synthesen in der hydroaromatischen Reihe, VIII. Mitteilung: Dien-Synthesen
des Anthracens. Anthracen-Forme". Justus Liebigs Annalen der Chemie. 486: 191–202.
doi:10.1002/jlac.19314860110 ([Link]
Diels, O.; Alder, K. (1931). "Synthesen in der hydroaromatischen Reihe, IX. Mitteilung: Synthese des
Camphenilons und des Santens". Justus Liebigs Annalen der Chemie. 486: 202–210.
doi:10.1002/jlac.19314860111 ([Link]
Diels, O.; Alder, K. (1931). "Synthesen in der hydroaromatischen Reihe, X. Mitteilung: "Dien-Synthesen"︁
mit Pyrrol und seinen Homologen". Justus Liebigs Annalen der Chemie. 486: 211–225.
doi:10.1002/jlac.19314860112 ([Link]
Diels, O.; Alder, K. (1931). "Synthesen in der hydroaromatischen Reihe, XI. Mitteilung. ("Dien-
Synthesen"︁des Cyclopentadiens, Cyclo-hexadiens und Butadiens mit Acetylen-dicarbonsäure und ihren
Estern". Justus Liebigs Annalen der Chemie. 490: 236–242. doi:10.1002/jlac.19314900109 ([Link]
rg/10.1002%2Fjlac.19314900109).
Diels, O.; Alder, K. (1931). "Synthesen in der hydroaromatischen Reihe, XII. Mitteilung. ("Dien-
Synthesen"︁sauerstoffhaltiger Heteroringe. 2. Dien-Synthesen des Furans.)". Justus Liebigs Annalen der
Chemie. 490: 243–257. doi:10.1002/jlac.19314900110 ([Link]
Diels, O.; Alder, K. (1931). "Synthesen in der hydroaromatischen Reihe, XIII. Mitteilung. ("Dien-
Synthesen"︁sauerstoffhaltiger Heteroringe. 3. Dien-Synthesen der Cumaline.)". Justus Liebigs Annalen
der Chemie. 490: 257–266. doi:10.1002/jlac.19314900111 ([Link]
1).
Diels, O.; Alder, K. (1931). "Synthesen in der hydroaromatischen Reihe, XIV. Mitteilung. ("Dien-
Synthesen"︁stickstoffhaltiger Heteroringe. 2. Dien-Synthesen der Pyrrole mit Acetylen-dicarbonsäure
und mit ihren Estern.)". Justus Liebigs Annalen der Chemie. 490: 267–276.
doi:10.1002/jlac.19314900112 ([Link]
Diels, O.; Alder, K. (1931). "Synthesen in der hydroaromatischen Reihe, XV. Mitteilung. ("Dien-
Synthesen"︁stickstoffhaltiger Heteroringe. 3. Dien-Synthesen der Indole.)". Justus Liebigs Annalen der
Chemie. 490: 277–294. doi:10.1002/jlac.19314900113 ([Link]
Diels, O.; Alder, K. (1932). "Synthesen in der hydroaromatischen Reihe, XVI. Mitteilung. ("Dien-
Synthesen"︁stickstoffhaltiger Heteroringe. 4. Dien-Synthesen der Pyrrole, Imidazole und Pyrazole.)".
Justus Liebigs Annalen der Chemie. 498: 1–15. doi:10.1002/jlac.19324980102 ([Link]
2Fjlac.19324980102).
 Diels, O.; Alder, K. (1932). "Synthesen in der hydroaromatischen Reihe, XVII. Mitteilung. ("Dien-
Synthesen"︁stickstoffhaltiger Heteroringe. 5. Dien-Synthesen des Pyridins, Chinolins, Chinaldins und
Isochinolins.)". Justus Liebigs Annalen der Chemie. 498: 16–49. doi:10.1002/jlac.19324980103 ([Link]
[Link]/10.1002%2Fjlac.19324980103).
Diels, O.; Alder, K. (1933). "Synthesen in der hydroaromatischen Reihe, XVIII "Dien-Synthesen"︁
stickstoffhaltiger Heteroringe. 6. Dien-Synthesen des Pyridins. Zur Kenntnis des Chinolizins, Indolizins,
Norlupinans und Pseudolupinins". Justus Liebigs Annalen der Chemie. 505: 103–150.
doi:10.1002/jlac.19335050109 ([Link]
Diels, O.; Alder, K. (1934). "Synthesen in der hydroaromatischen Reihe, XIX. "Dien-Synthesen"︁
stickstoffhaltiger Heteroringe. 7. Zur Kenntnis der Primärprodukte bei den Dien-Synthesen des Pyridins,
Chinolins und Chinaldins". Justus Liebigs Annalen der Chemie. 510: 87–128.
doi:10.1002/jlac.19345100106 ([Link]
Diels, O.; Reese, J. (1934). "Synthesen in der hydroaromatischen Reihe, XX. Über die Anlagerung von
Acetylen-dicarbonsäureester an Hydrazobenzol". Justus Liebigs Annalen der Chemie. 511: 168–182.
doi:10.1002/jlac.19345110114 ([Link]
Diels, O.; Meyer, R. (1934). "Synthesen in der hydroaromatischen Reihe, XXI. "Dien-Synthesen"︁
stickstoffhaltiger Heteroringe. 8. Über den Verlauf der Dien-Synthese des Pyridins in
methylalkoholischer Lösung". Justus Liebigs Annalen der Chemie. 513: 129–145.
doi:10.1002/jlac.19345130108 ([Link]
Diels, O.; Friedrichsen, W. (1934). "Synthesen in der hydroaromatischen Reihe, XXII. Über die
Anthracen–C4O3-Addukte, ihre Eignung zu Dien-Synthesen und ein neues Prinzip zur Synthese von
Phtalsäuren und Dihydro-phtalsäuren". Justus Liebigs Annalen der Chemie. 513: 145–155.
doi:10.1002/jlac.19345130109 ([Link]
Diels, O.; Möller, F. (1935). "Synthesen in der hydroaromatischen Reihe, XXIII. "Dien-Synthesen"︁
stickstoffhaltiger Heteroringe. 9. Stilbazol und Acetylen-dicarbonester". Justus Liebigs Annalen der
Chemie. 516: 45–61. doi:10.1002/jlac.19355160104 ([Link]
Diels, O.; Kech, H. (1935). "Synthesen in der hydroaromatischen Reihe, XXIV "Dien-Synthesen"︁
stickstoffhaltiger Heteroringe". Justus Liebigs Annalen der Chemie. 519: 140–146.
doi:10.1002/jlac.19355190112 ([Link]
Diels, O.; Reese, J. (1935). "Synthesen in der hydroaromatischen Reihe, XXV Über die Addukte aus
Acetylen-dicarbonsäureester und Hydrazo-Verbindungen (2)". Justus Liebigs Annalen der Chemie. 519:
147–157. doi:10.1002/jlac.19355190113 ([Link]
Diels, O.; Harms, J. (1935). "Synthesen in der hydroaromatischen Reihe, XXVI. "Dien-Synthesen"︁
stickstoffhaltiger Heteroringe. 11. Über die aus Isochinolin und Acetylen-dicarbonsäureester
entstehenden Addukte". Justus Liebigs Annalen der Chemie. 525: 73–94. doi:10.1002/jlac.19365250107
([Link]
Diels, O.; Schrum, H. (1937). "Synthesen in der hydroaromatischen Reihe,XXVII. "Dien-Synthesen"︁
stickstoffhaltiger Heteroringe. 12. Über den Abbau der "gelben Substanz"︁zu einem Isomeren des
Norlupinans (1-Methyl-octahydro-indolizin)". Justus Liebigs Annalen der Chemie. 530: 68–86.
doi:10.1002/jlac.19375300106 ([Link]
Diels, O.; Pistor, H. (1937). "Synthesen in der hydroaromatischen Reihe, XXVIII. "Dien-Synthesen"︁
stickstoffhaltiger Heteroringe. 13. α-Picolin und Acetylen-dicarbonsäureeste". Justus Liebigs Annalen
der Chemie. 530: 87–98. doi:10.1002/jlac.19375300107 ([Link]
63. "The Nobel Prize in Chemistry 1950" ([Link]
The Nobel Foundation. Retrieved 19 February 2016.
64. Berson, Jerome A. (1992). "Discoveries missed, discoveries made: creativity, influence, and fame in
chemistry" ([Link] Tetrahedron. 48 (1): 3–
17. doi:10.1016/S0040-4020(01)80574-3 ([Link]
ISSN 0040-4020 ([Link]
65. Zincke, Th.; Günther, H. (1893). "Ueberführung von Pentenderivaten in Indenderivate" ([Link]
[Link]/books?id=FepAAAAAYAAJ&pg=RA1-PA243). Justus Liebigs Annalen der Chemie (in German). 272
(3): 243–270. doi:10.1002/jlac.18932720302 ([Link] ISSN 1099-
0690 ([Link]
66. Zincke, Th. (1897). "Ueber die Einwirkung von Chlor auf o-Amidophenole und o-Diamine" ([Link]
[Link]/books?id=mhe1vM4JliAC&pg=PA135). Justus Liebigs Annalen der Chemie (in German). 296 (2):
135–158. doi:10.1002/jlac.18972960202 ([Link] ISSN 1099-0690
([Link]
67. Zincke, Th.; Meyer, Kurt H. (1909). "Ueber die Umwandlung von Pentenderivaten in Indenderivate" ([Link]
[Link]/work/o3ab7pbrpvfg3aghd73z3qvh2u/access/ia_file/crossref-pre-1923-scholarly-works/10.
1002%[Link]/10.1002%[Link]) (PDF). Justus Liebigs Annalen der
Chemie (in German). 367 (1–2): 1–13. doi:10.1002/jlac.19093670102 ([Link]
3670102). ISSN 1099-0690 ([Link]
68. Zincke, T. H.; Pfaffendorf, W. (1912). "Über Tetrachlor-o-kresol und seine Umwandlung in Perchlorindon" (ht
tps://[Link]/doi/10.1002/jlac.19123940103). Justus Liebigs Annalen der
Chemie (in German). 394 (1): 3–22. doi:10.1002/jlac.19123940103 ([Link]
40103). ISSN 1099-0690 ([Link]
69. О полимеризации двуэтиленовых углеводородов ([Link]
70. Harries, C. (1905). "Zur Kenntniss der Kautschukarten: Ueber Abbau und Constitution des Parakautschuks"
([Link]
orks/10.1002%[Link]/10.1002%[Link]) (PDF). Berichte der
deutschen chemischen Gesellschaft. 38 (1): 1195–1203. doi:10.1002/cber.190503801220 ([Link]
0.1002%2Fcber.190503801220). ISSN 1099-0682 ([Link]
71. Staudinger, Hermann (1912). Die ketene ([Link]
up) (in German). Stuttgart, F. Enke. p. 58.
72. v. Euler, H.; Josephson, K. O. (1920). "Über Kondensationen an Doppelbindungen. I.: Über die
Kondensation von Isopren mit Benzochinon" ([Link]
u/access/ia_file/crossref-pre-1923-scholarly-works/10.1002%[Link]/10.1002%252Fcb
[Link]) (PDF). Berichte der deutschen chemischen Gesellschaft (A and B Series). 53 (5):
822–826. doi:10.1002/cber.19200530517 ([Link] ISSN 1099-0682
([Link]
73. Albrecht, W. (1902). Über Cyclopentadiënchinone. Kondensationsversuche mit Diphenylmethan,
Dihydronaphtalin und Cyclopentadiën. Inaugural-Dissertation... von Walther Albrecht... P.
Stankiewicz'Buchdruckerei.
74. Albrecht, Walther (1906). "Additionsproducte von Cyklopentadiën und Chinonen" ([Link]
g/work/jqjwydt5o5hvflwad3elzfgoau/access/ia_file/crossref-pre-1909-scholarly-works/10.1002%252Fjlac.19
[Link]/10.1002%[Link]) (PDF). Justus Liebigs Annalen der Chemie (in
German). 348 (1–2): 31–49. doi:10.1002/jlac.19063480104 ([Link]
ISSN 1099-0690 ([Link]
75. Woodward, R. B.; Sondheimer, F.; Taub, D.; Heusler, K.; McLamore, W. M. (1952). "The Total Synthesis of
Steroids". Journal of the American Chemical Society. 74 (17): 4223–4251. doi:10.1021/ja01137a001 (http
s://[Link]/10.1021%2Fja01137a001).
76. Corey, E. J.; Weinshenker, N. M.; Schaaf, T. K.; Huber, W. (1969). "Stereo-controlled synthesis of
prostaglandins F-2a and E-2 (dl)". Journal of the American Chemical Society. 91 (20): 5675–7.
doi:10.1021/ja01048a062 ([Link] PMID 5808505 ([Link]
[Link]/5808505).
77. Danishefsky, S.; Hirama, M.; Fritsch, N.; Clardy, J. (1979). "Synthesis of disodium prephenate and disodium
epiprephenate. Stereochemistry of prephenic acid and an observation on the base-catalyzed rearrangement
of prephenic acid to p-hydroxyphenyllactic acid". Journal of the American Chemical Society. 101 (23):
7013–7018. doi:10.1021/ja00517a039 ([Link]
78. Wender, P. A.; Schaus, J. M.; White, A. W. (1980). "General methodology for cis-hydroisoquinoline
synthesis: Synthesis of reserpine". Journal of the American Chemical Society. 102 (19): 6157–6159.
doi:10.1021/ja00539a038 ([Link]
79. Martin, S. F.; Rueger, H.; Williamson, S. A.; Grzejszczak, S. (1987). "General strategies for the synthesis of
indole alkaloids. Total synthesis of (±)-reserpine and (±)-α-yohimbine". Journal of the American Chemical
Society. 109 (20): 6124–6134. doi:10.1021/ja00254a036 ([Link]
80. Nicolaou, K. C.; Yang, Z.; Liu, J. J.; Ueno, H.; Nantermet, P. G.; Guy, R. K.; Claiborne, C. F.; Renaud, J.;
Couladouros, E. A.; Paulvannan, K.; Sorensen, E. J. (1994). "Total synthesis of taxol". Nature. 367 (6464):
630–4. Bibcode:1994Natur.367..630N ([Link]
doi:10.1038/367630a0 ([Link] PMID 7906395 ([Link]
gov/7906395). S2CID 4371975 ([Link]
81. Narasaka, K.; Shimada, S.; Osoda, K.; Iwasawa, N. (1991). "Phenylboronic Acid as a Template in the Diels-
Alder Reaction". Synthesis. 1991 (12): 1171–1172. doi:10.1055/s-1991-28413 ([Link]
-1991-28413).
82. Smith, A. B.; Sestelo, J. P.; Dormer, P. G. (1995). "Total Synthesis of (−)-Furaquinocin C". Journal of the
American Chemical Society. 117 (43): 10755–10756. doi:10.1021/ja00148a023 ([Link]
ja00148a023).
83. Kozmin, S. A.; Rawal, V. H. (1998). "A General Strategy to Aspidosperma Alkaloids: Efficient,
Stereocontrolled Synthesis of Tabersonine". Journal of the American Chemical Society. 120 (51): 13523–
13524. doi:10.1021/ja983198k ([Link]
84. Gibbs, R. A.; Okamura, W. H. (1988). "A short enantioselective synthesis of (+)-sterpurene: Complete
intramolecular transfer of central to axial to central chiral elements". Journal of the American Chemical
Society. 110 (12): 4062–4063. doi:10.1021/ja00220a069 ([Link]
85. Charest, M. G.; Siegel, D. R.; Myers, A. G. (2005). "Synthesis of (-)-tetracycline". Journal of the American
Chemical Society. 127 (23): 8292–3. doi:10.1021/ja052151d ([Link]
PMID 15941256 ([Link]
86. Dauben, W. G.; Kessel, C. R.; Takemura, K. H. (1980). "Simple, efficient total synthesis of cantharidin via a
high-pressure Diels–Alder reaction". Journal of the American Chemical Society. 102 (22): 6893–6894.
doi:10.1021/ja00542a060 ([Link]
87. Holmes, H. L. (1948). "The Diels–Alder Reaction Ethylenic and Acetylenic Dienophiles". Organic Reactions.
Vol. 4. pp. 60–173. doi:10.1002/0471264180.or004.02 ([Link]
ISBN 978-0471264187.
88. Butz, L. W.; Rytina, A. W. (1949). "The Diels–Alder Reaction Quinones and Other Cyclenones". Organic
Reactions. Vol. 5. pp. 136–192. doi:10.1002/0471264180.or005.03 ([Link]
0.or005.03). ISBN 978-0471264187.
89. Kloetzel, M. C. (1948). "The Diels–Alder Reaction with Maleic Anhydride". Organic Reactions. Vol. 4. pp. 1–
59. doi:10.1002/0471264180.or004.01 ([Link] ISBN 978-
0471264187.
90. Heintzelman, G. R.; Meigh, I. R.; Mahajan, Y. R.; Weinreb, S. W. (2005). "Diels-Alder Reactions of Imino
Dienophiles". Organic Reactions. Vol. 65. pp. 141–599. doi:10.1002/0471264180.or065.02 ([Link]
0.1002%2F0471264180.or065.02). ISBN 978-0471264187.
91. Ciganek, E. (1984). "The Intramolecular Diels-Alder Reaction". Organic Reactions. Vol. 32. pp. 1–374.
doi:10.1002/0471264180.or032.01 ([Link] ISBN 978-
0471264187.

Bibliography
Carey, Francis A.; Sundberg, Richard J. (2007). Advanced Organic Chemistry: Part B: Reactions and
Synthesis (5th ed.). New York: Springer. ISBN 978-0387683546.

External links
[1] ([Link] English Translation of Diels and Alder's seminal 1928 German
article that won them the Nobel prize. English title: 'Syntheses of the hydroaromatic series'; German title
"Synthesen in der hydroaromatischen Reihe".

Retrieved from "[Link]