Chiral Bis-π-allylpalladium Complex Catalyzed Asymmetric Allylation of Imines:  Enhancement of the Enantioselectivity and Chemical Yield in the Presence of Water

• Published in: Journal of the American Chemical Society Vol. 125; no. 46; pp. 14133 - 14139
• Main Authors: Fernandes, Rodney A, Stimac, Anton, Yamamoto, Yoshinori
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 19.11.2003; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Multidisciplinary; Exact sciences and technology; Kinetics and mechanisms; Organic chemistry; Physical Sciences; Reactivity and mechanisms; Science & Technology; ALLYLSTANNANES; OLEFINS; ALDEHYDES; ORGANOMETALLIC REAGENTS; DOUBLE-BOND; ESTERS; Catalytic reaction; Enantioselectivity; Palladium Complexes; Catalyst selectivity; Transition metal Complexes; Imine; Complex catalyst; Experimental study; Allylation; Asymmetric reaction; Reaction mechanism; Platinoid Complexes; Tin Organic compounds; Catalyst activity; Organic stannane
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja037272x

The chiral π-allylpalladium complex 2a, prepared from exoethylidenenorpinane 7, catalyzed the allylation of diverse imines with allyltributylstannane in the presence of 1 equiv of water in good to high enantioselectivities. The catalyst prepared from a 1:1 mixture of (E)- and (Z)-7 was found to be consisting of two stereoisomers 2a and 2b in 1.3:1 ratio. On separation, 2a catalyzed the allylation of imines in much higher enantioselectivities than 2b, giving the same major enantiomer and thereby justifying the need to separate 2a free of 2b. We have achieved the highest separation ratio of >400:1 for 2a:2b by repeated recrystallizations. Isomerization of 2b to 2a during recovery of 2a from the filtrates was observed as more of 2a was recovered each time during recrystallization. Although dry THF was the best solvent, we tried various additives and found that addition of one equivalent of water gave the best results with respect to shorter reaction time, higher yields and enantioselectivities. Thus, we have developed a more general, reproducible, robust and a non-Lewis acid catalyzed procedure for catalytic asymmetric allylation of imines under essentially neutral conditions.