Direct catalytic asymmetric aldol additions of methyl ynones. Spontaneous reversal in the sense of enantioinduction.
J Am Chem Soc. 2004 Mar 10; 126(9):2660-1.JA

Abstract

In this Communication, we report the direct, catalytic, asymmetric aldol addition of methyl ynones using our dinuclear zinc catalyst. A spontaneous reversal in the sense of enantioinduction was observed for these reactions; formation of the (S)-enantiomer is favored in the early stages (69% ee after 5 min), whereas the (R)-enantiomer is isolated as the major product after prolonged reaction times (97% ee after 22 h). It could be shown that this reversal in enantioselectivity is due to formation of a new catalytic species which incorporates the aldol product.

Authors+Show Affiliations

Trost BM

Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA. bmtrost@stanford.edu

Fettes A

No affiliation info available

Shireman BT

No affiliation info available

MeSH

AlcoholsAldehydesAlkynesCatalysisKetonesStereoisomerism

Pub Type(s)

Journal Article

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

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

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

Language

eng

PubMed ID

14995157

Citation

Trost, Barry M., et al. "Direct Catalytic Asymmetric Aldol Additions of Methyl Ynones. Spontaneous Reversal in the Sense of Enantioinduction." Journal of the American Chemical Society, vol. 126, no. 9, 2004, pp. 2660-1.

Trost BM, Fettes A, Shireman BT. Direct catalytic asymmetric aldol additions of methyl ynones. Spontaneous reversal in the sense of enantioinduction. J Am Chem Soc. 2004;126(9):2660-1.

Trost, B. M., Fettes, A., & Shireman, B. T. (2004). Direct catalytic asymmetric aldol additions of methyl ynones. Spontaneous reversal in the sense of enantioinduction. Journal of the American Chemical Society, 126(9), 2660-1.

Trost BM, Fettes A, Shireman BT. Direct Catalytic Asymmetric Aldol Additions of Methyl Ynones. Spontaneous Reversal in the Sense of Enantioinduction. J Am Chem Soc. 2004 Mar 10;126(9):2660-1. PubMed PMID: 14995157.

* Article titles in AMA citation format should be in sentence-case

TY - JOUR T1 - Direct catalytic asymmetric aldol additions of methyl ynones. Spontaneous reversal in the sense of enantioinduction. AU - Trost,Barry M, AU - Fettes,Alec, AU - Shireman,Brock T, PY - 2004/3/5/pubmed PY - 2004/5/12/medline PY - 2004/3/5/entrez SP - 2660 EP - 1 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 126 IS - 9 N2 - In this Communication, we report the direct, catalytic, asymmetric aldol addition of methyl ynones using our dinuclear zinc catalyst. A spontaneous reversal in the sense of enantioinduction was observed for these reactions; formation of the (S)-enantiomer is favored in the early stages (69% ee after 5 min), whereas the (R)-enantiomer is isolated as the major product after prolonged reaction times (97% ee after 22 h). It could be shown that this reversal in enantioselectivity is due to formation of a new catalytic species which incorporates the aldol product. SN - 0002-7863 UR - https://www.unboundmedicine.com/medline/citation/14995157/Direct_catalytic_asymmetric_aldol_additions_of_methyl_ynones__Spontaneous_reversal_in_the_sense_of_enantioinduction_ DB - PRIME DP - Unbound Medicine ER -

Tags

Direct catalytic asymmetric aldol additions of methyl ynones. Spontaneous reversal in the sense of enantioinduction.J Am Chem Soc. 2004 Mar 10; 126(9):2660-1.JA