Highly concentrated catalytic asymmetric allylation of ketones.
[reaction: see text] We report the catalytic asymmetric allylation of ketones under highly concentrated reaction conditions with a catalyst generated from titanium tetraisopropoxide and BINOL (1:2 ratio) in the presence of isopropanol. This catalyst promotes the addition of tetraallylstannane to a variety of ketones to produce tertiary homoallylic alcohols in excellent yield (80-99%) with high enantioselectivities (79-95%). The resulting homoallylic alcohols can also be epoxidized in situ using tert-butyl hydroperoxide (TBHP) to afford cyclic epoxy alcohols in high yield (84-87%).
Wooten
Alfred J
AJ
P. Roy and Diana T. Vagelos Laboratories, University of Pennsylvania, Department of Chemistry, 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, USA.
Kim
Jeung Gon
JG
Walsh
Patrick J
PJ
D000438:Alcohols / Q000737:chemistry; D000498:Allyl Compounds / Q000138:chemical synthesis*; D002384:Catalysis; D004852:Epoxy Compounds / Q000737:chemistry; D007659:Ketones / Q000138:chemical synthesis*; D015394:Molecular Structure; D009284:Naphthols / Q000737:chemistry; D009942:Organometallic Compounds; D013237:Stereoisomerism; D017971:Tin Compounds / Q000737:chemistry; D014025:Titanium / Q000737:chemistry; D020122:tert-Butylhydroperoxide / Q000737:chemistry
D000438:Alcohols; D000498:Allyl Compounds; C406944:BINOL, naphthol; D004852:Epoxy Compounds; D007659:Ketones; D009284:Naphthols; D009942:Organometallic Compounds; D017971:Tin Compounds; C031525:stannane; C102815:titanium isopropoxide; D020122:tert-Butylhydroperoxide; D014025:Titanium