Toggle Main Menu Toggle Search

Open Access padlockePrints

Asymmetric platinum group metal-catalyzed carbonyl-ene reactions: Carbon-carbon bond formation versus isomerization

Lookup NU author(s): Dr Simon DohertyORCiD, Dr Julian Knight, Catherine Smyth, Dr Ross Harrington, Emeritus Professor Bill CleggORCiD


Full text for this publication is not currently held within this repository. Alternative links are provided below where available.


A comparative study of the carbonyl-ene reaction between a range of 1,1′-disubstituted or trisubstituted alkenes and ethyl trifluoropyruvate catalyzed by Lewis acid-platinum group metal complexes of the type [M{(R)-BINAP}]2+ (M = Pt, Pd, Ni; BINAP is 2,2′- bis(diphenylphosphino)-1,1′-binaphthyl) revealed subtle but significant differences in their reactivity. For instance, the palladium-based Lewis acid [Pd{(R)-BINAP}]2+ catalyzes the ene reaction between methylene cycloalkane to afford the expected α-hydroxy ester in good yield and excellent diastereo- and enantioselectivity. In contrast, under the same conditions, the corresponding [M{(R)-BINAP}]2+ (M = Pt, Ni) catalyzes isomerization of methylene cycloalkane and the ene reaction of the resulting mixture of methylene cycloalkane and 1-methylcycloalkene at similar rates to afford a range of α-hydroxy esters in high regioselectivity, good diastereoselectivity, and good to excellent enantioselectivity. In addition, [Pt{(R)-BINAP}]2+ also catalyzes postreaction isomerization of the ene product as well as consecutive ene reactions to afford a double carbonyl-ene product. The sense of asymmetric induction has been established by single-crystal X-ray crystallography, and a stereochemical model consistent with the formation of (S)-configured α-hydroxy ester has been proposed; the same model also accounts for the observed exo-diastereoselectivity as well as the level of diastereoselectivity. © 2006 American Chemical Society.

Publication metadata

Author(s): Doherty S, Knight JG, Smyth CH, Harrington RW, Clegg W

Publication type: Article

Publication status: Published

Journal: Journal of Organic Chemistry

Year: 2006

Volume: 71

Issue: 26

Pages: 9751-9764

ISSN (print): 0022-3263

ISSN (electronic): 1520-6904

Publisher: American Chemical Society


DOI: 10.1021/jo062023n

PubMed id: 17168594


Altmetrics provided by Altmetric