Stereoselective Synthesis of 4-Hydroxy-1-Silyl-1-Allenylboranes and Access to 2-Silylethynyl-1,3-Diols

被引：0

作者：

Brahim, Ichrak El Haj ^{[1
,2
]}

Dridi, Islem Ishak ^{[1
,2
]}

Abderrahim, Raoudha ^{[2
]}

Chemla, Fabrice ^{[1
]}

Ferreira, Franck ^{[1
]}

Jackowski, Olivier ^{[1
]}

Perez-Luna, Alejandro ^{[1
]}

机构：

[1] Sorbonne Univ, Inst Parisien Chim Mol, CNRS, 4 Pl Jussieu, F-75005 Paris, France

[2] Univ Carthage, Fac Sci Bizerte, Lab Phys Materiaux Lamellaires & Nanomateriaux Hyb, Bizerte 7021, Tunisia

来源：

ASIAN JOURNAL OF ORGANIC CHEMISTRY | 2024年 / 13卷 / 05期

关键词：

allenylboranes; allenylsilanes; silylboration; stereoselectivity; synthesis; GEM-SILYLBORYLATION; ENANTIOENRICHED ALLENYLSILANES; 1,4-HYDROSILYLATION; HYDROSILYLATION; PROPARGYLATION; ALLENYLATION; ACTIVATION; EPOXIDES; REAGENTS; KETONES;

D O I：

10.1002/ajoc.202400042

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The highly stereoselective gem-silylboration of chiral 2-substituted 1-ethynylepoxides is reported herein. The reaction involves first the deprotonation of the epoxides in the acetylenic position followed by transmetallation with Et3SiBpin. The transient silylborane ate-complexes generated undergo the stereoselective 1,2-migration of the Et3Si-group to the sp-hybridized terminus carbon of the ethynyl-moiety in a stereospecific anti-addition. The moisture-sensitive and thermally unstable 4-hydroxy-1-triethylsilyl-1-allenyl(pinacolato)boranes thus obtained react with aldehydes through an SE2'-mode of addition, affording highly functionalized 2-triethysilylethynyl-1,3-diols with a good diastereoselectivity which is rationalized by a Yamamoto-Houk type transition state model. The stereoselective and stereospecific gem-silylborylation of chiral trans 2-substituted 1-ethynylepoxides affords (aS*,S*)-4-hydroxy-1-silyl-1-allenylboranes. The reaction of theses gem-bimetallic species with aldehydes gives access to highly functionalized (anti,syn)-2-triethysilylethynyl-1,3-diols with a good diastereoselectivity. image

引用

页数：7

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