Synthesis and Structure of 2,2′ ‐Boryl‐, Germyl‐Silyl‐, and Stannyl‐Substituted 1,1′ ‐Binaphthyl Systems
作者:Birgit Schilling、Dieter E. Kaufmann、Volkier Kaiser
DOI:10.1002/cber.19971300718
日期:1997.7
path to the binaphthylmonoboronic acid ester 9 is opened up. A further increase in the quantity of electrophile also leads to the binaphthylbisboronic acid ester 12. The 2,2′-disubstituted silyl, germyl, and stannyl derivatives 13a-15a are accessible in good yields. Treatment with boron halides leads exclusively to methyl/halogen exchange, giving the bidentate Lewis acids 13b-15b, the former of which can
通过2,2'-二溴-1,1'-联萘基(5)的锂化反应,合成了许多在2-或2,2'-位取代的路易斯酸联萘系统。逐步锂化并随后用硼酸三甲酯进行硼化,生成溴化硼酸6,可通过与频哪醇酯化7来稳定溴化硼酸。通过将反应混合物增加至2当量。正丁基锂和2当量 硼酸甲酯打开了通向二萘基单硼酸酯9的路径。亲电子试剂的量的进一步增加也导致了联萘基双硼酸酯12。2,2'-二取代的甲硅烷基,癸基和苯乙烯基衍生物13a-15a产量高。治疗卤化硼引线排他地涉及甲基/卤素交换,给予二齿路易斯酸13B-15B,其中前者可通过oxygen.Only在双(三丁基锡烷基)联萘的情况下,桥接16A不本位取代发生在存在三氯化硼,得到双(二氯硼基)取代的双萘基16b,然后可以将其水解为11。通过X射线衍射研究了大多数化合物的结构。对于2,2'-二取代的化合物13a-15a萘基彼此垂直取向。分子内和分子间的相互作用受该双萘基系统的控