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. 2007 Dec 7;72(25):9772-5.
doi: 10.1021/jo701633k. Epub 2007 Nov 14.

Asymmetric synthesis of 2 degrees- and 3 degrees-Carbinols via B-methallyl-10-(TMS and Ph)-9-borabicyclo[3.3.2]decanes

José G Roman  1 , John A Soderquist
Affiliations

Asymmetric synthesis of 2 degrees- and 3 degrees-Carbinols via B-methallyl-10-(TMS and Ph)-9-borabicyclo[3.3.2]decanes

José G Roman et al. J Org Chem. .

Abstract

Simple Grignard procedures provide methallylboranes 1a and 1b in enantiomerically pure form from air-stable precursors in 98% and 95% yields, respectively. These reagents add smoothly to aldehydes and methyl ketones, respectively, providing branched 2 degrees- (6, 69-89%, 94-99% ee) and 3 degrees- (10, 71-87%, 74-96% ee) homoallylic alcohols.

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Figures

Figure 1
Figure 1
Proposed models for the most energetically favorable pre-transition state complexes which explain the observed stereochemistry in the methallylboration of RCHO with 1a (A) and RCOMe with 1b (B).
Scheme 1
Scheme 1
Preparation of Methallylborane 1.
Scheme 2
Scheme 2
Asymmetric Allylboration of Aldehydes with 1a.
Scheme 3
Scheme 3
Asymmetric Allylboration of Benzaldimine with 1a.
Scheme 4
Scheme 4
Asymmetric Allylboration of Ketones with 1b.
Scheme 5
Scheme 5
Ozonolysis of β-Methyl Homoallylic Alcohols.
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