Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, UK.
Org Lett. 2012 Aug 17;14(16):4278-81. doi: 10.1021/ol3020607. Epub 2012 Aug 6.
Ring-closing iodoamination of tert-butyl 2-hydroxy-7-[N-methyl-N-(α-methyl-p-methoxybenzyl)amino]cyclohept-3-ene-1-carboxylates proceeds with concomitant loss of the N-α-methyl-p-methoxybenzyl group to give the corresponding 8-azabicyclo[3.2.1]octane scaffolds in >99:1 dr. Subsequent elaboration of one of these templates provided access to (+)-pseudococaine hydrochloride, in seven steps and 31% overall yield from commercially available starting materials.
叔丁基 2-羟基-7-[N-甲基-N-(α-甲基-对甲氧基苄基)氨基]环己-3-烯-1-羧酸酯的闭环碘胺化反应伴随着 N-α-甲基-对甲氧基苄基的同时离去，得到相应的 8-氮杂双环[3.2.1]辛烷支架，立体选择性大于 99:1。对其中一个模板的进一步修饰提供了（+）-伪可卡因盐酸盐，从商业可得的起始原料出发，经过七步反应，总收率为 31%。
