Journal ArticleDOI
2-Carbomethoxy-1,3-butadiene: an electronically activated diene in [4 + 2] cycloadditions with electron-deficient dienophiles
Claude Spino,Jason Crawford +1 more
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TLDR
In this article, cross-diels-alder reactions between 2-carbomethoxy-1,3-butadiene and electron-rich dienes were carried out.Abstract:
Cross Diels–Alder reactions between 2-carbomethoxy-1,3-butadiene 1 and electron-rich dienes were carried out. It was found that diene 1 had a higher reactivity than even the well-known Danishefsky diene in its Diels–Alder cycloaddition with electron-deficient dienophiles. In addition, (Z)-1-methylthio-3-carbomethoxy-1,3-butadiene 11 was found to have a higher reactivity than (Z)-1-methylthio-1,3-butadiene and (Z)-2-carbomethoxy-1,3-hexadiene, while both (E)- and (Z)-1,2-(bis)-carbomethoxy-1,3-butadiene 14 reacted efficiently with maleic anhydride to give the corresponding cy-cloadduct 15.read more
Citations
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Journal ArticleDOI
An understanding of the electrophilic/nucleophilic behavior of electro-deficient 2,3-disubstituted 1,3-butadienes in polar diels-alder reactions. A density functional theory study.
TL;DR: A study of the global electrophilicity pattern of the reagents at the ground state allows us to rationalize the participation of electron-deficient 2-susbtituted and 2,3-disubstituted 1-3-butadienes as nucleophiles in polar Diels-Alder reactions.
Journal ArticleDOI
An enyne metathesis/(4 + 2)-dimerization route to (+/-)-differolide.
TL;DR: A concise total synthesis of (+/-)-differolide has been achieved by enyne metathesis of allyl propynoate using the Grubbs initiator 4 and the hypothesis that low concentration of ruthenium species and high concentration of enyne substrate would be advantageous was found.
Journal ArticleDOI
Characteristics of the Two Frontier Orbital Interactions in the Diels−Alder Cycloaddition
TL;DR: It was shown that the dissymmetry in electron-rich dienophiles increases their reactivities, and it was demonstrated that in the case of normal Diels-Alder cycloadditions, the FMO theory could predict the relative reactivities between diensophiles, while in the cases of inverse-electron demand Diels -Alder reactions, it could not.
Journal ArticleDOI
Why do Electron‐Deficient Dienes React Rapidly in Diels−Alder Reactions with Electron‐Deficient Ethylenes? A Density Functional Theory Analysis
TL;DR: In this paper, the electron-deficient (ED) dimethyl 2,3-dimethylenesuccinate with two electron-rich (ER) and two ED ethylenes has been studied at the B3LYP/6-31G* level of theory.
Reference EntryDOI
The Retro–Diels–Alder Reaction Part I. C ? C Dienophiles
TL;DR: A comprehensive review of the literature on retro Diels-Alder reactions can be found in this article, with a focus on expelling C-C dienophiles, i.e. those reactions that generate a new carbon-carbon double or triple bond in the dienophile.
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Dihydrothiophenes, part VIII. 2-Carbomethoxy-1,3-butadiene: a convenient synthesis of a stable precursor and a survey of its Diels-Alder reactions
Synthesis and High-Pressure Diels-Alder Cycloadditions of 6-Methoxycarbonyl-3-oxo-2-azabicyclo(2.2.0)hex-5-ene.
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