26118-97-8Relevant articles and documents
Efficient synthesis of sordidin, a male pheromone compound emitted by Cosmopolites sordidus
Ducrot, Paul-Henri
, p. 3923 - 3928 (1996)
A multigram-scale synthesis of sordidin ((1S*,3R*,5R*,7S*) 2,8-dioxa 1-ethyl 3,5,7-trimethyl bicyclo [3,2,1] octane) is described. Sordidin is obtained as a racemic mixture of its four isomers 1a-d (10 steps, 27% overall yield).
On the regioselectivity and diastereoselectivity of ACC hydrazone alkylation
Huynh, Uyen,Uddin, Md. Nasir,Wengryniuk, Sarah E.,McDonald, Stacey L.,Coltart, Don M.
supporting information, p. 432 - 436 (2017/01/13)
The asymmetric α-allylation of 3-pentanone using several different N-amino cyclic carbamate (ACC) auxiliaries is described. The level of asymmetric induction was found to range from er?=?93:7 to er?=?99:1. The factors that lead to compromised selectivity
Origins of stereoselectivity in the α-alkylation of chiral hydrazones
Krenske, Elizabeth H.,Houk,Lim, Daniel,Wengryniuk, Sarah E.,Coltart, Don M.
supporting information; experimental part, p. 8578 - 8584 (2011/03/20)
Density functional theory calculations and experiment reveal the origin of stereoselectivity in the deprotonation-alkylation of chiral N-amino cyclic carbamate (ACC) hydrazones. When the ACC is a rigid, camphor-derived carbamate, the two conformations of the azaenolate intermediate differ in energy due to conformational effects within the oxazolidinone ring and steric interactions between the ACC and the azaenolate. An electrophile adds selectively to the less-hindered π-face of the azaenolate. Although it was earlier reported that use of ACC auxiliaries led to α-alkylated ketones with er values of 82:18 to 98:2, B3LYP calculations predict higher stereoselectivity. Direct measurement of the dr of an alkylated hydrazone prior to removal of the auxiliary confirms this prediction; the removal of the auxiliary under the reported conditions can compromise the overall stereoselectivity of the process.
