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A one-pot diastereoselective synthesis of cis-3-hexene-1,6-diols via an unusually reactive organozinc intermediate.
J Am Chem Soc. 2003 Mar 19; 125(11):3210-1.JA

Abstract

A highly diastereoselective method for the synthesis of cis-3-hexene-1,6-diols has been developed. This new reaction proceeds with excellent control of diastereoselectivity over four stereocenters and the double bond geometry. The diols are made in a one-pot procedure involving hydroboration of a terminal alkyne and transmetalation to zinc to give a divinylzinc intermediate. This intermediate undergoes reductive elimination, forming a C=C bond. In the absence of a trapping reagent, diene is liberated (70% yield); however, in the presence of ketones or aldehydes, the proposed intermediate metallocyclopentene is trapped via a double insertion of the carbonyl substrate. Workup provides the diols in 47-86% yield.

Authors+Show Affiliations

García C
P. Roy and Diane T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, PA 19104-6323, USA.
Libra ER
No affiliation info available
Carroll PJ
No affiliation info available
Walsh PJ
No affiliation info available

MeSH

AlcoholsAldehydesAlkenesAlkynesKetonesOrganometallic CompoundsStereoisomerismSubstrate SpecificityZinc

Pub Type(s)

Journal Article
Research Support, U.S. Gov't, P.H.S.

Language

eng

PubMed ID

12630865

Citation

García, Celina, et al. "A One-pot Diastereoselective Synthesis of Cis-3-hexene-1,6-diols Via an Unusually Reactive Organozinc Intermediate." Journal of the American Chemical Society, vol. 125, no. 11, 2003, pp. 3210-1.
García C, Libra ER, Carroll PJ, et al. A one-pot diastereoselective synthesis of cis-3-hexene-1,6-diols via an unusually reactive organozinc intermediate. J Am Chem Soc. 2003;125(11):3210-1.
García, C., Libra, E. R., Carroll, P. J., & Walsh, P. J. (2003). A one-pot diastereoselective synthesis of cis-3-hexene-1,6-diols via an unusually reactive organozinc intermediate. Journal of the American Chemical Society, 125(11), 3210-1.
García C, et al. A One-pot Diastereoselective Synthesis of Cis-3-hexene-1,6-diols Via an Unusually Reactive Organozinc Intermediate. J Am Chem Soc. 2003 Mar 19;125(11):3210-1. PubMed PMID: 12630865.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - A one-pot diastereoselective synthesis of cis-3-hexene-1,6-diols via an unusually reactive organozinc intermediate. AU - García,Celina, AU - Libra,Eric R, AU - Carroll,Patrick J, AU - Walsh,Patrick J, PY - 2003/3/13/pubmed PY - 2003/5/17/medline PY - 2003/3/13/entrez SP - 3210 EP - 1 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 125 IS - 11 N2 - A highly diastereoselective method for the synthesis of cis-3-hexene-1,6-diols has been developed. This new reaction proceeds with excellent control of diastereoselectivity over four stereocenters and the double bond geometry. The diols are made in a one-pot procedure involving hydroboration of a terminal alkyne and transmetalation to zinc to give a divinylzinc intermediate. This intermediate undergoes reductive elimination, forming a C=C bond. In the absence of a trapping reagent, diene is liberated (70% yield); however, in the presence of ketones or aldehydes, the proposed intermediate metallocyclopentene is trapped via a double insertion of the carbonyl substrate. Workup provides the diols in 47-86% yield. SN - 0002-7863 UR - https://www.unboundmedicine.com/medline/citation/12630865/A_one_pot_diastereoselective_synthesis_of_cis_3_hexene_16_diols_via_an_unusually_reactive_organozinc_intermediate_ DB - PRIME DP - Unbound Medicine ER -