TY - JOUR
T1 - Allylic functionalization of unactivated olefins with grignard reagents
AU - Bao, Hongli
AU - Bayeh, Liela
AU - Tambar, Uttam K.
PY - 2014/2/3
Y1 - 2014/2/3
N2 - New advances in the functionalization of unactivated olefins with carbon nucleophiles have provided more efficient and practical approaches to convert inexpensive starting materials into valuable products. Recent examples have been reported with stabilized carbon nucleophiles, tethered carbon nucleophiles, diazoesters, and trifluoromethane donors. A general method for functionalizing olefins with aromatic, aliphatic, and vinyl Grignard reagents was developed. In a one-pot process, olefins are oxidized by a commercially available reagent to allylic electrophiles, which undergo selective copper-catalyzed allylic alkylation with Grignard reagents. Products are formed in high yield and with high regioselectivity. This was utilized to synthesize a series of skipped dienes, a class of compounds that are prevalent in natural products and are difficult to synthesize by known allylic alkylation methods. It all begins with olefins: Allylic functionalization with carbon nucleophiles is a powerful strategy for converting unactivated olefins into complex products. A general method for functionalizing olefins with aromatic, aliphatic, and vinyl Grignard reagents was developed. In a one-pot process, olefins are oxidized by a commercially available reagent to allylic electrophiles, which undergo selective copper-catalyzed allylic alkylation with Grignard reagents.
AB - New advances in the functionalization of unactivated olefins with carbon nucleophiles have provided more efficient and practical approaches to convert inexpensive starting materials into valuable products. Recent examples have been reported with stabilized carbon nucleophiles, tethered carbon nucleophiles, diazoesters, and trifluoromethane donors. A general method for functionalizing olefins with aromatic, aliphatic, and vinyl Grignard reagents was developed. In a one-pot process, olefins are oxidized by a commercially available reagent to allylic electrophiles, which undergo selective copper-catalyzed allylic alkylation with Grignard reagents. Products are formed in high yield and with high regioselectivity. This was utilized to synthesize a series of skipped dienes, a class of compounds that are prevalent in natural products and are difficult to synthesize by known allylic alkylation methods. It all begins with olefins: Allylic functionalization with carbon nucleophiles is a powerful strategy for converting unactivated olefins into complex products. A general method for functionalizing olefins with aromatic, aliphatic, and vinyl Grignard reagents was developed. In a one-pot process, olefins are oxidized by a commercially available reagent to allylic electrophiles, which undergo selective copper-catalyzed allylic alkylation with Grignard reagents.
KW - Grignard reaction
KW - alkenes
KW - allylic compounds
KW - copper
KW - homogeneous catalysis
UR - http://www.scopus.com/inward/record.url?scp=84893446940&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84893446940&partnerID=8YFLogxK
U2 - 10.1002/anie.201309134
DO - 10.1002/anie.201309134
M3 - Article
C2 - 24458538
AN - SCOPUS:84893446940
SN - 1433-7851
VL - 53
SP - 1664
EP - 1668
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 6
ER -