Regio- and enantioselective control in the reactions of alpha-(N-carbamoyl)alkylcuprates with allylic phosphates.
Alpha-(N-carbamoyl)alkylcuprates (RCuCNLi or R2CuLi) react with allylic phosphates to afford homoallylic amines in good chemical yields. Regioselectivity is governed by steric factors in both the cuprate reagent and phosphate substrate and systems can be designed to give either the S(N)2' or S(N)2 substitution product cleanly. Excellent enantioselectivities can be achieved with either a scalemic alpha-di[(N-carbamoyl)alkyl]cuprate and an achiral phosphate or with a scalemic allylic phosphate and an achiral cuprate reagent. [reaction: see text]
Howard L. Hunter Laboratory, Department of Chemistry, Clemson University, Clemson, SC 29634-1905, USA.
R Karl
RK
Dieter
Vinayak K
VK
Gore
Ningyi
N
Chen
D000498:Allyl Compounds / Q000737:chemistry*; D000588:Amines / Q000138:chemical synthesis; D003300:Copper / Q000737:chemistry*; D008094:Lithium / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010710:Phosphates / Q000737:chemistry*; D013237:Stereoisomerism
D000498:Allyl Compounds; D000588:Amines; D009942:Organometallic Compounds; D010710:Phosphates; D003300:Copper; D008094:Lithium