Published October 14, 2009 | Version Accepted Version + Supplemental Material
Journal Article Open

Asymmetric Carbon−Carbon Bond Formation γ to a Carbonyl Group: Phosphine-Catalyzed Addition of Nitromethane to Allenes

  • 1. ROR icon Massachusetts Institute of Technology

Abstract

A chiral phosphine catalyzes the addition of a carbon nucleophile to the γ position of an electron-poor allene (amide-, ester-, or phosphonate-substituted), in preference to isomerization to a 1,3-diene, in good ee and yield. This strategy provides an attractive method for the catalytic asymmetric γ functionalization of carbonyl (and related) compounds.

Additional Information

© 2009 American Chemical Society. Received August 4, 2009. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences, Grant R01-GM57034), Merck Research Laboratories, and Novartis. We thank Dr. Nicolas Marion for assistance, Evonik Degussa for providing samples of phosphepines 1−4, and Prof. Qi-Lin Zhou for providing a precursor to phosphine 5. Funding for the MIT Department of Chemistry Instrumentation Facility has been furnished in part by NIH IS10RR13886 and NSF DBI-9729592.

Attached Files

Accepted Version - nihms147483.pdf

Supplemental Material - ja9061823_si_001.pdf

Files

ja9061823_si_001.pdf

Files (3.1 MB)

Name Size
md5:6364cae62443f18b654ed39b93fce38f
2.4 MB Preview Download
md5:059904280b9aa605d8d411fca26f641f
640.1 kB Preview Download

Additional details

Identifiers

PMCID
PMC2758928
Eprint ID
102867
DOI
10.1021/ja9061823
Resolver ID
CaltechAUTHORS:20200428-095147086

Related works

Describes
10.1021/ja9061823 (DOI)

Funding

NIH
R01-GM57034
Merck Research Laboratories
Novartis
NIH
IS10RR13886
NSF
DBI-9729592

Dates

Created
2020-04-28
Created from EPrint's datestamp field
Updated
2021-11-16
Created from EPrint's last_modified field