One-pot Multicomponent Coupling Methods for the Synthesis of Diastereo- and Enantioenriched (Z)-trisubstituted Allylic Alcohols

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2009 May 30

PMID 19476375

Citations 12

Authors

Michael H Kerrigan

Sang-Jin Jeon

Young K Chen

Luca Salvi

Patrick J Carroll

Patrick J Walsh

Affiliations

Soon will be listed here.

Abstract

(Z)-trisubstituted allylic alcohols are widespread structural motifs in natural products and biologically active compounds but are difficult to directly prepare. Introduced herein is a general one-pot multicomponent coupling method for the synthesis of (Z)-alpha,alpha,beta-trisubstituted allylic alcohols. (Z)-trisubstituted vinylzinc reagents are formed in situ by initial hydroboration of 1-bromo-1-alkynes. Addition of dialkylzinc reagents induces a 1,2-metalate rearrangement that is followed by a boron-to-zinc transmetalation. The resulting vinylzinc reagents add to a variety of prochiral aldehydes to produce racemic (Z)-trisubstituted allylic alcohols. When enantioenriched aldehyde substrates are employed, (Z)-trisubstituted allylic alcohols are isolated with high dr (>20:1 in many cases). For example, vinylation of enantioenriched benzyl-protected alpha- and beta-hydroxy propanal derivatives furnished the expected anti-Felkin addition products via chelation control. Surprisingly, silyl-protected alpha-hydroxy aldehydes also afford anti-Felkin addition products. A protocol for the catalytic asymmetric addition of (Z)-trisubstituted vinylzinc reagents to prochiral aldehydes with a (-)-MIB-based catalyst has also been developed. Several additives were investigated as inhibitors of the Lewis acidic alkylzinc halide byproducts, which promote the background reaction to form the racemate. Alpha-ethyl and alpha-cyclohexyl (Z)-trisubstituted allylic alcohols can now be synthesized with excellent levels of enantioselectivity in the presence of diamine inhibitors.

Citing Articles

Access to stereodefined (Z)-allylsilanes and (Z)-allylic alcohols via cobalt-catalyzed regioselective hydrosilylation of allenes.

Wang C, Teo W, Ge S Nat Commun. 2017; 8(1):2258.

PMID: 29273720 PMC: 5741631. DOI: 10.1038/s41467-017-02382-7.

Diastereoselective chelation-controlled additions to β-silyloxy aldehydes.

Stanton G, Kauffman M, Walsh P Org Lett. 2012; 14(13):3368-71.

PMID: 22721430 PMC: 3401491. DOI: 10.1021/ol301354w.

Highly stereoselective C-C bond formation by rhodium-catalyzed tandem ylide formation/[2,3]-sigmatropic rearrangement between donor/acceptor carbenoids and chiral allylic alcohols.

Li Z, Parr B, Davies H J Am Chem Soc. 2012; 134(26):10942-6.

PMID: 22694052 PMC: 3413634. DOI: 10.1021/ja303023n.

Highly diastereoselective chelation-controlled additions to α-silyloxy ketones.

Stanton G, Koz G, Walsh P J Am Chem Soc. 2011; 133(20):7969-76.

PMID: 21534530 PMC: 3112462. DOI: 10.1021/ja201629d.

Synthesis of quaternary carbon stereogenic centers through enantioselective Cu-catalyzed allylic substitutions with vinylaluminum reagents.

Gao F, McGrath K, Lee Y, Hoveyda A J Am Chem Soc. 2010; 132(40):14315-20.

PMID: 20860365 PMC: 2951504. DOI: 10.1021/ja106829k.

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