Tertiary α‐Silyl Alcohols by Diastereoselective Coupling of 1,3‐Dienes and Acylsilanes Initiated by Enantioselective Copper‐Catalyzed Borylation

Abstract

An efficient synthesis of functionalizedt ertiary asilyl alcohols by an enantio-and diastereoselective coppercatalyzedthree-component coupling of 1,3-dienes,bis(pinacolato)diboron, and acylsilanes is reported. The reaction proceeds well with different 1,3-dienes and abroad range of arylas well as alkenyl-but also alkyl-substituted acylsilanes.T he target compounds are formed with high regio-, diastereo-, and enantioselectivity (up to 99 %eeand d.r. > 20:1) and are highly versatile synthetic building blocks.

Recent advances in Cu-catalyzed C(sp3)–Si and C(sp3)–B bond formation

“…An unusual type of reaction has been described in which an acyl silane reacts with 1,3-dienes, under Cu catalysis, leading to an interesting class of α-silyl tertiary alcohols (Scheme 44) [82]. In most cases, high chemical yields along with high ees were obtained when phosphoramidite ligand L28 was used.…”

Catalytic asymmetric addition of thiols to silyl glyoxylates for synthesis of multi-hetero-atom substituted carbon stereocenters

“…Recently, Oestreich developed the stereoselective addition of chiral allylic copper intermediates ( in situ generated from boron nucleophile and 1,3-dienes) to acylsilanes (path iii). 8 Alternatively, Wang, Han and co-workers realized an organocatalytic (vinylogous) aldol reaction with carbonyl compounds as nucleophiles (path iv). 9 The advance in synthesis of chiral α-silyl alcohols by using “carbon” nucleophiles intrigued us to investigate enantioselective construction of multi-hetero-atom-bearing carbon stereogenic centers by using hetero-atom nucleophiles.…”

A unified approach for divergent synthesis of contiguous stereodiads employing a small boronyl group

“…In the past few years, a number of catalytic approaches to boronyl-containing 1,2-stereodiads have been reported by Miura, Ito, Liao, Brown, and other groups [31][32][33][34][35][36][37][38][39][40][41][42][43][44] . However, usually only one diastereomer rather than the other is preferred, and development of general and reliable methodologies for obtaining all possible stereoisomers of β-boron carbonyls remains highly challenging [45][46][47][48][49][50] .…”