Institute of Organic Chemistry, University of Mainz, Duesbergweg 10-14, 55128 Mainz, Germany.
J Org Chem. 2011 Dec 2;76(23):9777-84. doi: 10.1021/jo201871c. Epub 2011 Oct 26.
Under controlled conditions, 6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline-1-carbonitrile can be quantitatively deprotonated in the α-position. Its alkylation directly furnishes 3,4-dihydroisoquinolines which can serve as starting materials for the preparation of various alkaloids. Here, the preparation of the benzylisoquinolines (+)-laudanidine, (+)-armepavine, and (+)-laudanosine as well as the tetrahydroprotoberberines (-)-corytenchine and (-)-tetrahydropseudoepiberberine using Noyori's asymmetric transfer hydrogenation are described. The dimeric alkaloids (+)-O-methylthalibrine and (+)-tetramethylmagnolamine were obtained from nonracemic precursors in Ullmann diaryl ether syntheses.
在受控条件下，6,7-二甲氧基-1,2,3,4-四氢异喹啉-1-甲腈可以在α-位定量脱质子化。其烷基化直接生成 3,4-二氢异喹啉，可作为制备各种生物碱的起始原料。在这里，描述了使用 Noyori 的不对称转移氢化法制备苯并异喹啉 (+)-劳丹碱、(+)-阿朴啡碱和 (+)-劳丹醇，以及四氢原小檗碱 (-)-考来替林和 (-)-四氢巴马汀。非对映体前体通过乌尔曼二芳基醚合成法获得了二聚生物碱 (+)-O-甲基他布林和 (+)-四甲基木兰碱。
