Diastereoselective production of homoallylic alcohols bearing quaternary centers from gamma-substituted allylic indiums and ketones.
Highly stereoselective In-employed addition of gamma-substituted allylic halides (cyclohexenyl halides, cinnamyl halides, and ethyl 4-bromocrotonate) to ketones is established to produce homoallyl alcohols bearing quaternary centers. The reactivity patterns and relative stability of allylic indiums were studied. The addition of water characteristically affected the reactions. Cyclohexenyl indium addition was completely disturbed, but a clear reaction was observed in the cinnamyl and crotonate-indium addition. In the case of ethyl 4-bromocrotonate, an interesting conversion of a gamma-adduct into an alpha-adduct was observed in anhydrous conditions.
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan. baba@chem.eng.osaka-u.ac.jp
Srinivasarao Arulananda
SA
Babu
Makoto
M
Yasuda
Akio
A
Baba
D000438:Alcohols / Q000138:chemical synthesis* / Q000737:chemistry; D000498:Allyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D007204:Indium / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D013237:Stereoisomerism
D000438:Alcohols; D000498:Allyl Compounds; D007659:Ketones; D009942:Organometallic Compounds; D007204:Indium