Stereoselective synthesis of hexahydroisobenzofuran-4(1H)-ones from chiral substituted cyclohex-2-enyl carbamates via asymmetric homoaldol reaction and THF cyclocondensation

被引：7

作者：

Becker, Jochen ^{[1
]}

Froehlich, Roland ^{[1
]}

Kataeva, Olga ^{[1
]}

Hoppe, Dieter ^{[1
]}

机构：

[1] Univ Munster, Inst Organ Chem, D-48149 Munster, Germany

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2007年 / 2007卷 / 20期

关键词：

asymmetric synthesis; heterocycles; metallated allyl carbamates; homoaldol reactions; tetrahydrofuran synthesis; SECONDARY ALLYLTITANIUM(IV) REAGENTS; ENANTIOSELECTIVE SYNTHESIS; STEREOCHEMICAL COURSE; LITHIATION ADJACENT; SCLEROPHYTIN-A; TITANIUM; DIASTEREOSELECTIVITY; ALDEHYDES; NITROGEN; ACID;

D O I：

10.1002/ejoc.200700220

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The diastereofacial selectivity of the homoaldol reaction of metalated substituted cyclohex-2-enyl carbamates with aldehydes is controlled by the nature of the metal complex. Allyl-lithiums yield syn-configured products whereas transmetallation to Ti(NEt2)(3) gives access to anti-configured 3-(1-hydroxyalkyl)cyclohexenes. The syn-configured homoaldol products were transformed into annulated all-cis-tetrahydrofurans by Lewis acid-mediated cyclocondensation with aldehydes. Analogous cis,trans,cis-substituted hexahydroisobenzofuran-4(1H)-ones, the core structure of many biologically active natural products, were synthesized starting from anti-configured homoaldol products. The configurations of the products were determined by H-1 NMR coupling constants, nOe-studies, and X-ray crystal structure analysis. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007).

引用

页码：3349 / 3364

页数：16

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