Science of Synthesis

Han, J. W.; Hayashi, T., Science of Synthesis: Stereoselective Synthesis, (2011) 1, 923.

General Introduction

Palladium-catalyzed asymmetric hydrosilylation of C=C bonds is one of the most efficient methodologies to give enantiomerically enriched organosilicon compounds, which are useful intermediates in stereoselective organic synthesis.[‌1‌–‌6‌] The hydrosilylation of simple alkenes, such as styrene and oct-1-ene with trichlorosilane, provides chiral alkylsilanes ‌1‌, which are transformed into chiral alcohols ‌2‌ by way of oxidative cleavage with retention of configuration, and that of conjugated 1,3-dienes provides chiral allylsilanes ‌3‌, which are transformed into chiral homoallylic alcohols ‌4‌ by way of the diastereoselective reaction with carbonyl compounds (‌Scheme 1‌).[‌7‌–‌10‌] In addition, double hydrosilylation of norbornadiene followed by oxidation provides enantiomerically enriched diol ‌5‌, which is a versatile intermediate for asymmetric synthesis of useful chiral molecules, such as (+)-sparteine (‌6‌) and chiral norbornadiene ligand ‌7‌ (‌Scheme 1‌).[‌11‌–‌13‌]

‌Meeeee 8‌ Meeeee Meeeeee ee Meeeeeeeee Meeeeeeeeeeeeee[‌8‌–‌88‌]

Mee eeeeeeeee-eeeeeeeee eeeeeeeeee eeeeeeeeeeeeeee ee M=M eeeee eee eeee eeeeeeee eeeeeeeee eeeeeeeeeeeeee eeeeeeeeeeeee ee eeeeeeeeeeeeeee eeeeeeeee, eee ee eeee e eeee eeee-eeeeeeeee eeeeeeee, eeeee ee ee ee eeeeeeee eeeeeee eee eeeeeee eeeeeeee eeee e eee eeeeeeee eeeeeee eee eeeeeee eee eeeeeee. Meeeeee, eeee eeeeee ee eeeee ee e eeeee-eeeee eeeeeeeeeee ee eeeeee eeeeeeeeeeeee eee ee eee eeeeeeeeee eeeeee ee eee eeeeeeee eee eee eee ee eeeeeeee eeeeeeeeeeeeeee (ee 88 °M).[‌88‌]

Me eee eeeeee ee e eeeee ee eeeeeeeee-eeeeeeeee eeeeeeeeee eeeeeeeeeeeeeee ee eeeeeee, eeeeeee eeeeee eeeeeeeeeee eeeeeeeee eeeeeee eeee eeee eeeeeeeee eee eeeeeeeee eeee eeeeeeeee eeeeeeeeee eee eeeeeeeeeeeeeeeeeeee. Meeeeee, eee ee e eeeeeeeee eeeeeeeeeeee eeeeee, eeee ee 8,8′-eee(eeeeeeeeeeeeeeeee)-8,8′-eeeeeeeeee (‌8‌), eeeee ee eeeee eeeeeeeee eeeeeeee eeee eee ee eeeeeeeeeee eeeeeeeee eeeeeee ee eee eeeeeeeeeeeeeee.[‌88‌] Mee MMM eeeeeee ‌8‌–‌88‌, eeeeee eeeeeeeeee eeeee eeeeeeeee,[‌88‌,‌88‌] eeeeeeeeee eeeeeee ‌88‌–‌88‌, eeeeee eeeeee eeeeeeeee,[‌88‌–‌88‌] eee eeeeeeeeeeeeeee eeeeee ‌88‌, eeeeee e eeeeeeeeee eeeeee,[‌88‌] eeeeee eeee eeeeeeeee eeeeeeeeee eee eeeeeeeeeeeeeeeeeeee ee eee eeeeeeee (‌Meeeee 8‌).

‌Meeeee 8‌ 8,8′-Mee(eeeeeeeeeeeeeeeee)-8,8′-eeeeeeeeee eee Meeeee Meeeeeeeeee Meeeeeeee eee Meeeeeeeeeeeeee Meeeeee eee Meeeeeeeeeeeeee[‌88‌–‌88‌]

Meeee eeeee eeeeee eeeeeeeeeee eeeeeeeee eeeeeee, MMM eeeeeee ‌8‌–‌88‌ eeeee eee, eeeee eeee eee eeeeeee eeeeeee ee eeeeeeeeeee ee eeeeeeeeeee eeeee ee eee 8′-eeeeeeee ee eee eeeeeeeeee eeeeeeee; ee eeeeeeee, eeeee eee eee eeeeeeee eee eeeeeeeee eeeee. Mee eeeeeeeeeee eeeeeee ee eee eeeeeeeeeeeeeee eeeeeeeee ee eeeeeeeee/MMM eeeeeeeee ee eeee eee eeeeeeeeeeeeeeeeeeee eeee eeeeeeeeeeee eeeeeeeee ee eee eeeeeeeee eeee, eeeeeeee eee eeeeeeeee eeeeeeee eeee eee eeeeee eeee eeee (‌Meeee 8‌). Mee eeeeeee, 8-(eeeeeeeeeeeeeeeee)-8′-eeeeeee-8,8′-eeeeeeeeee (‌8‌, MeM-MMM), eeeee ee eee eeee eeeeee eee eeeee-eeeeeeeeeee eeeeeee, eeeeeee eeee eeeee eeeeeeeeeeeeeeeeee eeee 8-(eeeeeeeeeeeeeeeee)-8,8′-eeeeeeeeee (‌88‌, M-MMM) ee eee eeeeeeeeeeeeeee ee eeeeeee (‌Meeee 8‌, eeeeeee 8 eee 8).[‌88‌,‌88‌,‌88‌] Me eee eeee ee eee eeeeeeeeeeeeeee ee eeeeeeeeeeeeeee, 8-(eeeeeeeeeeeeeeeee)-8′-(8,8-eeeeeeee-8-eeeeeeeeeeeee)-8,8′-eeeeeeeeee (‌88‌, Me-MMM) eeeee eeee eeeeee eeeeeeeeeeeeeeeeee eeee MeM-MMM (‌8‌) eee M-MMM (‌88‌) (eeeeeee 8–8).[‌88‌,‌88‌]

‌Meeee 8‌ Meeeeeeee-Meeeeeeee Meeeeeeeee Meeeeeeeeeeeeee ee M=M Meeee eeee Meeeeeeeeeeeeee Meeee MMM Meeeeee[‌88‌,‌88‌–‌88‌]

Meeee	M8	M8	MMM Meeeee	Meee (°M)	Meee (e)	ee (%)	Meeee (%)	Mee
8	Me	M	‌8‌	8	88	88	888	[‌88‌]
8	Me	M	‌88‌	−88	88	88	88	[‌88‌]
8	(MM8)8Me	M	‌8‌	88	88	88	88	[‌88‌]
8			‌8‌	88	88	88	888	[‌88‌]
8			‌88‌	88	8	88	88	[‌88‌]
8			‌88‌	8	88	88	88	[‌88‌]

References