Ashweek Neil J, Coldham Iain, Haxell Thomas F, Howard Steven
School of Chemistry, University of Exeter, Stocker Road, Exeter, UK EX4 4QD.
Org Biomol Chem. 2003 May 7;1(9):1532-44. doi: 10.1039/b301502e.
The synthesis of chiral 1,2-diamines and 1,3-diamines was achieved from the unsubstituted diamines by way of N-tert-butoxycarbonyl (Boc) substituted imidazolidines (tetrahydroimidazoles) and pyrimidines (hexahydro-1,3-diazines), which were treated with sec-butyllithium to effect deprotonation alpha- to the N-Boc group, followed by addition of an electrophile to give substituted products that could be hydrolysed under acidic conditions to give the substituted 1,2- or 1,3-diamines. Use of the chiral ligand (-)-sparteine promoted asymmetric deprotonation of the imidazolidine substrates to give, after hydrolysis, enantiomerically enriched 1,2-diamines.
通过N-叔丁氧羰基（Boc）取代的咪唑烷（四氢咪唑）和嘧啶（六氢-1,3-二嗪），由未取代的二胺实现手性1,2-二胺和1,3-二胺的合成。将这些化合物用仲丁基锂处理，使N-Boc基团的α位去质子化，然后加入亲电试剂得到取代产物，该产物在酸性条件下可水解得到取代的1,2-或1,3-二胺。使用手性配体（-）-鹰爪豆碱可促进咪唑烷底物的不对称去质子化，水解后得到对映体富集的1,2-二胺。
