A Convenient Method for the Preparation of Some Optically Active Allylic Alcohols¹

Oxidation (Hydroxylation and Acyloxylation) via C‐H Bond Activation

“…In order to avoid a regiochemical problem in hydrogen atom abstraction, most studies of this asymmetric allylic oxidation have been examined with cycloalkenes as substrates which impose no regiochemical problem. In 1965, Denny et al for the first time reported a catalytic asymmetric KharaschSosnovsky reaction by using Cu(I1)-(@)-ethyl camphorate as a catalyst, though enantioselectivity was low (Scheme 9) [21]. A quarter of a century later, natural or synthetic amino acids were introduced as chiral auxiliaries and much improved enantioselectivity (up to 65% ee) was achieved (Scheme 10) [22].…”

New chiral bidentate ligands containing thiazolyl and pyridyl donors for copper-catalyzed asymmetric allylic oxidation of cyclohexene

“…The copper-catalyzed allylic oxidation (KharashSosnovsky reaction) of olefins with peresters has been the subject of numerous synthetic and mechanistic investigations [1][2][3][4][5][6][7][8][9][10]. The allylic ester product of the reaction can easily be converted into allylic alcohol by saponification or reduction method.…”

Optically pure (S)-cyclopent-2-en-1-ol and (S)-3-methoxycyclopentene

“…After eight recrystallizations and regeneration of the succinate, followed by LiA1H4 reduction, the specific rotation of 1 was [a];' +22.g0 (c 5, CC14), corresponding to about 15% ee. Denney et al (2) achieved partial asymmetric induction in the reaction of cyclopentadiene with tert-butylhydroperoxide and the cupric salt of (+)-a-ethyl camphorate, and obtained a-ethyl-P-A2-cyclopentenyl camphorate, which upon LiA1H4 reduction yielded 1, [a]z6 -13.6" (c 8.9, CHCl,). Asami and Kirihara (3) reported that the asymmetric transformation of cyclopentene oxide with lithium (S) -2-[(pyrrolidin -1 -yl)-methy]]pyrrolidide gave 1 in 49% yield and 3 1 % ee, [ a ] ; ' -55" (c 1.35, CC14).…”