Vargas-Díaz M Elena, Joseph-Nathan Pedro, Tamariz Joaquín, Zepeda L Gerardo
Departamento de Química OrgAnica, Escuela Nacional de Ciencias Biológicas, Instituto Politécnico Nacional, Prol. de Carpio y Plan de Ayala, México, D.F., 11340 Mexico.
Org Lett. 2007 Jan 4;9(1):13-6. doi: 10.1021/ol062319f.
[reaction: see text] The new macrocycle 9 (>70% yield from hydroxythiol 10) was treated with several nucleophilic reagents (RMgX, RLi, and LiAlH4) affording carbinols 12a-j (80-96% yield, >99:1 dr). Oxidative hydrolysis of 12a,c,e, followed by LiAlH4 reduction of the resulting mixture, gave 16a,c,e in >95% ee,16c being a key precursor for the preparation of fungicide 17. The absolute configuration of 9 and 12j (Nu = H) was established by single-crystal X-ray diffraction analyses and chemical correlation.
[反应：见正文] 新的大环化合物9（由羟基硫醇10制备，产率>70%）与几种亲核试剂（RMgX、RLi和LiAlH₄）反应，得到甲醇12a - j（产率80 - 96%，非对映体比例>99:1）。12a、c、e经氧化水解，然后用LiAlH₄还原所得混合物，得到ee值>95%的16a、c、e，16c是制备杀菌剂17的关键前体。9和12j（Nu = H）的绝对构型通过单晶X射线衍射分析和化学关联确定。
