Control of Chemo-, Regio-, and Enantioselectivity in Copper Hydride Reductions of Morita-Baylis-Hillman Adducts

Roscoe T H Linstadt; Carl A Peterson; Carina I Jette; Zarko V Boskovic; Bruce H Lipshutz

doi:10.1021/acs.orglett.6b03464

Control of Chemo-, Regio-, and Enantioselectivity in Copper Hydride Reductions of Morita-Baylis-Hillman Adducts

Org Lett. 2017 Jan 20;19(2):328-331. doi: 10.1021/acs.orglett.6b03464. Epub 2017 Jan 11.

Authors

Roscoe T H Linstadt¹, Carl A Peterson¹, Carina I Jette¹, Zarko V Boskovic¹, Bruce H Lipshutz¹

Affiliation

¹ Department of Chemistry and Biochemistry, University of California , Santa Barbara, California 93106, United States.

PMID: 28075138
DOI: 10.1021/acs.orglett.6b03464

Abstract

Nonracemically ligated copper hydride can be used to effect tandem S_N2'/1,2-reductions of racemic Morita-Baylis-Hillman (MBH) acetates to access enantioenriched chiral allylic alcohols with defined olefin geometry. MBH esters, including those with β-substitution, can be transformed to stereodefined enoates by taking advantage of a bulky, oligomeric, in situ generated trialkoxysiloxane leaving group. Finally, an atypical conversion of easily arrived at MBH alcohol derivatives to nonracemic allylic alcohols is disclosed.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.