Stereoselectivity of the captodative alkenes 1-acetylvinyl arenecarboxylates in Diels-Alder reactions with cyclic dienes and stereospecific rearrangement of their bicyclo[2.2.n] α-ketol adducts

被引：1

作者：

Aguilar, Raul ^{[1
]}

Santoyo, Blanca M. ^{[1
]}

Zarate-Zarate, Daniel ^{[1
]}

Vazquez, Miguel A. ^{[2
]}

Padilla, Rosa M. ^{[1
]}

Jimenez-Vazquez, Hugo A. ^{[1
]}

Tamariz, Joaquin ^{[1
]}

机构：

[1] Inst Politecn Nacl, Escuela Nacl Ciencias Biol, Dept Quim Organ, Prol Carpio & Plan Ayala S-N, Mexico City 11340, DF, Mexico

[2] Univ Guanajuato, Dept Quim Organ, Div Ciencias Nat & Exactas, Noria Alta S-N, Guanajuato 36050, Gto, Mexico

来源：

ARABIAN JOURNAL OF CHEMISTRY | 2020年 / 13卷 / 01期

关键词：

Captodative alkenes; 1-Acetylvinyl p-nitrobenzoyloxy; alpha-Keto carbinols; alpha-Ketol rearrangement; Cascade process; mCPBA; 1,3-DIPOLAR CYCLOADDITION REACTIONS; ENANTIOSELECTIVE TOTAL-SYNTHESIS; SECONDARY ORBITAL INTERACTIONS; ASYMMETRIC-SYNTHESIS; KETENE EQUIVALENTS; TRANSITION-STATES; OLEFINS; REACTIVITY; CYCLOPENTADIENE; ACID;

D O I：

10.1016/j.arabjc.2017.08.008

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Captodative alkene 1-acetylvinyl p-nitrobenzenecarboxylate 1a was evaluated for its reactivity and stereoselectivity with cyclohexadiene (10) in Diels-Alder reactions, showing exclusive endo preference. The two hydrolyzed products of the endo and the exo adducts obtained from the Diels-Alder cycloaddition between 1a and cyclopentadiene (7) were 8b and 9b. When treated with mCPBA, a ring expansion took place to stereospecifically yield the novel 3-oxatricyclo[3.3.1.0(2,4)] nonanone acyloins 15 and 16, respectively. In the case of the alpha-ketol bicyclo[2.2.2]octanes 11b and 12b, the epoxidation/Baeyer-Villiger cascade process was preferred, resulting in the syn ketoepoxide 19b from each isomer. A synthetic application of this kind of transformation was carried out by reacting ketols 8b and 9b with an excess of mCPBA through a five-step cascade process to yield the bicyclic lactone 27 as a potential precursor of racemic b-carbaxylose. (C) 2017 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University.

引用

页码：900 / 915

页数：16