Enantioselective synthesis of butadien-2-ylcarbinols via (silylmethyl)allenic alcohols from chromium-catalyzed additions to aldehydes utilizing chiral carbazole ligands

被引：20

作者：

Duran-Galvan, Maria ^{[1
]}

Worlikar, Shilpa A. ^{[1
]}

Connell, Brian T. ^{[1
]}

机构：

[1] Texas A&M Univ, Dept Chem, College Stn, TX 77842 USA

来源：

TETRAHEDRON | 2010年 / 66卷 / 39期

关键词：

Asymmetric catalysis; Regioselectivity; Chromium; Dienes; Carbazole ligands; CYTOTOXIC CLERODANE DITERPENOIDS; ORGANOMETALLIC COMPOUNDS M=MG; ALPHA-ALLENIC BROMIDES; ASYMMETRIC CATALYSIS; AQUEOUS-MEDIA; REACTIVITY; 2-LITHIO-1,3-BUTADIENE; ALLENYLMETHYLSILANES; CHEMISTRY; REAGENT;

D O I：

10.1016/j.tet.2010.07.065

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The synthesis of chiral, nonracemic butadienylcarbinols by employing intermediate (trimethylsilyl) methylallenic alcohols is described. Allenic alcohols are obtained by treatment of aldehydes with (4-bromobut-2-ynyl)trimethylsilane in the presence of a catalytic amount of CrCl3 or CrCl2. Several new tridentate bis(oxazolinyl)carbazole ligands were synthesized and evaluated as the source of chirality. The synthesis of chiral allenic alcohols can be achieved in good yields (58-88%) and enantioselectivities (55-78% ee). Allenic alcohols may be treated with TBAF or 2 M HCl to provide the desired dienes in 43-86% yields. Alternatively, the (trimethylsilyl)methyl allenic alcohols afford iodobutadienyl carbinols when treated with N-iodosuccinimide. (C) 2010 Elsevier Ltd. All rights reserved.

引用

页码：7707 / 7719

页数：13

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