The transannular Diels–Alder strategy: applications to total synthesis

Marsault, Éric; Toró, András; Nowak, Paweł; Deslongchamps, Pierre

doi:10.1016/s0040-4020(01)00121-1

Cited by 174 publications

(87 citation statements)

References 102 publications

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“…[1] Intermolecular, [1] intramolecular [2] and transannular [3] variants are well documented. Given its importance, it is not surprising that the control of stereoselectivity of DielsϪAlder reactions continues to be an active area of research.…”

Section: Introductionmentioning

confidence: 99%

Stereocontrol of the Intramolecular Diels−Alder Reaction by Internal Hydrogen Bonding

2003

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A novel approach for exo/endo stereocontrol of intramolecular Diels−Alder reactions is described. Substrates carrying a hydroxymethyl group attached to the diene and an ester group attached to the dienophile participate in hydrogen bonding in the transition state. This non-covalent interaction causes either a significant enhancement or diminution in the observed kinetic endo/exo product ratio. Thus, the parent pentadienyl maleate 12 undergoes intramolecular Diels−Alder reaction to give an approx. 5:1 mixture of transand cis-fused bicyclic cycloadducts, whereas the C2-hydro-

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Section: Introductionmentioning

confidence: 99%

Stereocontrol of the Intramolecular Diels−Alder Reaction by Internal Hydrogen Bonding

2003

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“…Although the step count is similar to that of the only previous synthesis of this promising target (23 versus 24 steps for the longest linear route), [5] the new entry is considerably more productive (up to 3.3 %versus 0.41 %) and conceptually different. It illustrates the power of transannular functionalization, [11,40] aconcept that gains momentum to the extent that macrocycle formation becomes increasingly more facile,n ot least with the help of ever more mature (alkyne) Angewandte Chemie metathesis catalysts.F urthermore,t his project was initially conceived to showcase our growing confidence in p-acid catalysis,w hich still has al ong way to go in terms of applications to elaborate and highly precious substrates. [13] Though ultimately successful, the still rather empirical flavor of this topical field became apparent.…”

Section: Methodsmentioning

confidence: 99%

Concise Total Synthesis of Enigmazole A

et al. 2015

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An efficient entry into the phosphorylated marine macrolide enigmazoleAis described. Enigmazole Ainterferes with c-Kit signaling by an as yet unknown mode of action and is therefore ap otential lead in the quest for novel anticancer agents.K ey to success is ag old-catalyzed cascade comprising a[3,3]-sigmatropic rearrangement of apropargyl acetate along the periphery of am acrocyclic scaffold, followed by at ransannular hydroalkoxylation of the resulting transient allenyl acetate.This transformation mandated the use of achiral gold catalyst to ensure amatching double-asymmetric setting.Other noteworthy steps are the preparation of the oxazole building blockbyapalladium-catalyzed CÀHactivation, as well as the smooth ring-closing alkyne metathesis of ad iyne substrate bearing ap ropargylic leaving group,w hichh as only little precedent.

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“…82 O grupo de Jacobsen relata a reação TADA enantiosseletiva com elevado excesso enantiomérico, como etapa fundamental para a síntese de alguns sesquiterpenos (Esquema 34). 83 Bodwell e colaboradores publicaram a síntese de um sistema pentacíclico contendo dois átomos de nitrogênio, obtido através de reação TADA de demanda inversa eletrônica (Esquema 35).…”

Section: Reações Transanulares (Tada)unclassified