Premium
Room temperature and highly enantioselective additions of alkyltitanium reagents to aldehydes catalyzed by a titanium catalyst of ( R )‐h 8 ‐binol
Author(s) -
Li Qinghan,
Gau HanMou
Publication year - 2011
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.21018
Subject(s) - chemistry , nucleophile , enantioselective synthesis , catalysis , reactivity (psychology) , reagent , steric effects , nucleophilic addition , titanium , medicinal chemistry , organic chemistry , chirality (physics) , medicine , chiral symmetry breaking , alternative medicine , physics , pathology , quantum mechanics , nambu–jona lasinio model , quark
Three alkyltitanium reagents of RTi(O‐ i ‐Pr) 3 (R = Cy ( 1a ), i ‐Bu ( 1b ), and n ‐Bu ( 1c )) were prepared in good yields. The high‐resolution mass spectroscopy showed that 1b and 1 c in the gas phase are monomeric species. However, the solid state of 1a revealed a dimeric structure. Asymmetric additions of 1a , 1b , 1c to aldehydes catalyzed by a titanium catalyst of ( R )‐H 8 ‐BINOL were studied at room temperature. The reactions produced desired secondary alcohols in good yields with good to excellent enantioselectivities of up to 94% ee. Reactivity and enantioselectivity differences, in terms of steric bulkiness of the R nucleophiles, are herein described. The addition reactions of secondary c ‐hexyl to aldehydes were slower than the reactions of primary i ‐butyl or n ‐butyl nucleophiles. For the primary alkyls, lower enantioselectivities were obtained for products from addition reactions of the linear n ‐butyl as compared with the enantioselectivities of products from the addition reactions of the branched i ‐butyl group. The same stereochemistry of RTi(O‐ i ‐Pr) 3 addition reactions as the addition reactions of organozinc, organoaluminum, Grignard, or organolithium reagents directly supports the argument of that titanium‐catalyzed addition reactions of aldehydes involve an addition of an organotitanium nucleophile. Chirality, 2011. © 2011 Wiley‐Liss, Inc.