The Synthesis of Condensed Ring Compounds. VII. The Successful Use of Ethylene in the Diels—Alder Reaction<sup>1</sup>

Joshel, Lloyd M.; Butz, Lewis W.

doi:10.1021/ja01857a033

Cited by 38 publications

(23 citation statements)

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“…The preparaiioil of cycIohexene froin butadieile and eth~-lene was reported a number of years ago (30), but the Diels-Alder reaction as a route to deuterated cyclohexenes does not seem to have beell tried. For tlie synthesis of cyclohexenc-3,3,6,6-d4 the required reagents are ethylene and butadiene-l,l,4,4-d4.…”

Section: Results a S D Discussionmentioning

confidence: 99%

CYCLOHEXENE-3,3,6,6-d₄ A USEFUL COMPOUND FOR THE STUDY OF MECHANISM AND STRUCTURE

Wolfe¹,

Campbell²

1965

Can. J. Chem.

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The title compound (I) was prepared by Diels-Alder reaction of butadiene-1,1,4,4-d., with ethylene. The considerations which led to the synthesis of I are presented and some examples are then given of how use of I can simplify the study of, and provide new information about, a number of different kinds of problems. In the proton magnetic resonance (n.111.r.) spectra of the products of additions to I , the tertiary protons ~~s~~a l l y appear as clearly defined quartets. Since J J a n ! can be read directly from these spectra, both the stereochemistry of the additions and the conforn~ations of the products call be deduced. Thus, oxymercuration of I is clear!y a traws addition and Na/Hg reduction of the mercury takes place with retention of c o n f i g~~r a t~o~l . \hihe11 the second step is performed in D.0, the oxyn~ercuration-reduction sequence represents a convenient route for the trans addition of DOH to a double bond. Deuteroboration provided a n example of cis addition of DOH to I. Acid-catalyzed hydration of I resulted in scrambling of the d e~~t e r i u~n atoms. The value of Gn,/o~f is small; Gur/on is 600 cal/mole. The position of the double bond in a product resulting from allylic substitution of I is determined by integration of the n.m.r. spectrum. lielative to I, the possibilities are no rearrangement, 50% rearrangement, and 100% rearrangement of the double bond. The first product of allylic substitution by N-bro~nosuccinimide shows IIO rearrangement; therefore, this reaction does 11ot require a "free" radical intermediate. The structure of an adduct formed during allylic acetosylation of I by mercuric acetate (the Treibs reaction) has been determined.

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Section: Results a S D Discussionmentioning

confidence: 99%

CYCLOHEXENE-3,3,6,6-d₄ A USEFUL COMPOUND FOR THE STUDY OF MECHANISM AND STRUCTURE

Wolfe¹,

Campbell²

1965

Can. J. Chem.

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“…[15] The butadiene-ethene reaction and the butadiene dimerization require temperatures elevated to between 136 and 2008C, and pressures up to 80 atm, in the case of the butadieneethene reaction, to proceed. [2,16,17] Activation energies for these reactions were found to be 105.0 and 95.0 kJ mol 21 , respectively. [18] As the kinetic studies made no attempt to distinguish between the three mechanisms, the activation energies incorporate those of all the possible reaction pathways.…”

Section: Introductionmentioning

confidence: 94%

“…The butadiene‐ethene reaction and the butadiene dimerization require temperatures elevated to between 136 and 200°C, and pressures up to 80 atm, in the case of the butadiene‐ethene reaction, to proceed . Activation energies for these reactions were found to be 105.0 and 95.0 kJ mol −1 , respectively .…”

Section: Introductionmentioning

confidence: 99%

Active space and basis set effects in CASPT2 models of the 1,3‐butadiene‐ethene cycloaddition and the 1,3‐butadiene dimerization

Scarborough

Kobayashi

Thompson

et al. 2015

Int J of Quantum Chemistry

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The first step of the asynchronous biradical, stepwise biradical, and concerted mechanisms of the 1,3-butadiene Diels-Alder reactions with both ethene and itself was studied using CASPT2 to determine the influence of basis set and active space on reaction barriers. CASPT2(6,6) with the cc-pVDZ, 6-3111G(3df,2p) and cc-pVTZ basis sets provided the best results with average errors below 3.1 kJ mol 21 with respect to the experimental result. Increasing the active space size also had little effect on the calculated reaction barriers. With respect to experimental results, uncontracted multireference averaged quadratic coupled cluster (MRAQCC) produced superior barriers than internally contracted MRAQCC by 16.1-39.3 kJ mol 21 . The inability of CASSCF to locate transition states for some of the cycloadditions across the butadiene-ethene and butadiene dimerization reactions is also rationalized. CASPT2 suggests a preference for the concerted mechanism of the butadiene-ethene reaction, however, no basis set yielded a preference for any of the butadiene dimerization pathways.

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“…[24] Significantly, breakthrough of an intermolecular version of standard electron-demand Diels-Alder reaction was reported by Tririya and Zanger in 2004, to synthesize anthracyclinone precursor, where, an elegant example of cycloaddition between 1,3-butadiene and 1,4-benzoquinone were proceeded at room temperature leading to quantitative yield (see Figure 3). [25] In general, Diels À Alder reaction was well established with respect to mechanistic study, reactivity of diene and dienophile, and selectivity in product formation. However, Dethe et…”

Section: Introductionmentioning

confidence: 99%

Development and Applications of Double Diels‐Alder Reaction in Organic Synthesis

et al. 2021

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The class of Double Diels‐Alder (DDA) reactions leading the targets concisely where numerous synthetic pursuits have been rewarded with conceptually novel and streamlined methods. After the tremendous development and discoveries in various Diels‐Alder reactions including its key role applications in many natural products syntheses, the DDA reaction is considered as a growing branch of Diels‐Alder reaction where two consecutive [4+2] cycloadditions trigger the streamlined construction of polycyclic and macrocyclic architectures. In light of the ever‐increasing importance of DDA reactions in chemical sciences, we review the comprehensive studies and recent advances in DDA reactions in organic synthesis. This review summarizes key achievements of DDA for the preparation of macrocyclic, bicyclic, heterocyclic, and polycyclic structures documented since its revelation in 1980 to 2020. Emphasis is put on the synthesis of various structural classes based on the selectivity of the DDA reaction.

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The Synthesis of Condensed Ring Compounds. VII. The Successful Use of Ethylene in the Diels—Alder Reaction¹

Cited by 38 publications

References 0 publications

CYCLOHEXENE-3,3,6,6-d₄ A USEFUL COMPOUND FOR THE STUDY OF MECHANISM AND STRUCTURE

CYCLOHEXENE-3,3,6,6-d₄ A USEFUL COMPOUND FOR THE STUDY OF MECHANISM AND STRUCTURE

Active space and basis set effects in CASPT2 models of the 1,3‐butadiene‐ethene cycloaddition and the 1,3‐butadiene dimerization

Development and Applications of Double Diels‐Alder Reaction in Organic Synthesis

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The Synthesis of Condensed Ring Compounds. VII. The Successful Use of Ethylene in the Diels—Alder Reaction1

Cited by 38 publications

References 0 publications

CYCLOHEXENE-3,3,6,6-d4 A USEFUL COMPOUND FOR THE STUDY OF MECHANISM AND STRUCTURE

CYCLOHEXENE-3,3,6,6-d4 A USEFUL COMPOUND FOR THE STUDY OF MECHANISM AND STRUCTURE

Active space and basis set effects in CASPT2 models of the 1,3‐butadiene‐ethene cycloaddition and the 1,3‐butadiene dimerization

Development and Applications of Double Diels‐Alder Reaction in Organic Synthesis

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The Synthesis of Condensed Ring Compounds. VII. The Successful Use of Ethylene in the Diels—Alder Reaction¹

CYCLOHEXENE-3,3,6,6-d₄ A USEFUL COMPOUND FOR THE STUDY OF MECHANISM AND STRUCTURE

CYCLOHEXENE-3,3,6,6-d₄ A USEFUL COMPOUND FOR THE STUDY OF MECHANISM AND STRUCTURE