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. 2006 Aug 31;8(18):4089-91.
doi: 10.1021/ol061596j.

B-allenyl- and B-(gamma-trimethylsilylpropargyl)-10-phenyl-9-borabicyclo[3.3.2]decanes: asymmetric synthesis of propargyl and alpha-allenyl 3-degree-carbinols from ketones

Eliud Hernandez  1 , Carlos H Burgos, Eyleen Alicea, John A Soderquist
Affiliations

B-allenyl- and B-(gamma-trimethylsilylpropargyl)-10-phenyl-9-borabicyclo[3.3.2]decanes: asymmetric synthesis of propargyl and alpha-allenyl 3-degree-carbinols from ketones

Eliud Hernandez et al. Org Lett. .

Abstract

Simple and efficient Grignard procedures are reported for the syntheses of B-allenyl-10-(phenyl)-9-borabicyclo[3.3.2]decane (1) and its B-(gamma-trimethylsilylpropargyl) counterpart (2) in both enantiomeric forms. Both add selectively to ketones, providing propargyl- and alpha-silylallenyl 3-degree-carbinols, respectively (i.e., 6 (61-93% ee) and 9 (64-98% ee)). The air-stable boron byproduct is efficiently recovered and recycled back to either 1 or 2. The ozonolysis and bromination of 9 provide nonracemic alpha-hydroxy acids and gamma-bromopropynyl carbinols, respectively.

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Scheme 1
Scheme 2
Scheme 2
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