Jian Zhongbao, Kehr Gerald, Daniliuc Constantin G, Wibbeling Birgit, Erker Gerhard
Organisch-Chemisches Institut, Universität Münster, Corrensstr. 40, 48149 Münster, Germany.
Dalton Trans. 2017 Sep 12;46(35):11715-11721. doi: 10.1039/c7dt02315d.
The secondary aryl-P(H) phosphanyl substituted tert-butylacetylenes 7a,b (aryl: Mes or Mes*) undergo hydroboration with [HB(CF)] to give the geminal vinylidene-bridged P/B Lewis pairs 8a,b. The treatment of 8a,b with benzonitrile, N-sulfinylaniline, and phenyl isothiocyanate, respectively, gives the addition products 12a,b, 13a,b, and 14 with proton transfer from the phosphorus to the more basic nitrogen site. The reaction of the FLPs 8a,b with carbon dioxide yields a doubly boron bonded addition product. The reaction of 8b with a conjugated ynone formally proceeded by trans-1,2-hydrophosphination of the alkyne at the geminal FLP framework to give the seven-membered heterocycle 21.
二级芳基 - P(H)膦基取代的叔丁基乙炔7a,b（芳基：Mes或Mes*）与[HB(CF)]进行硼氢化反应，生成偕二乙烯叉桥连的P/B路易斯对8a,b。分别用苯甲腈、N-亚磺酰苯胺和苯基异硫氰酸酯处理8a,b，得到加成产物12a,b、13a,b和14，质子从磷转移到碱性更强的氮位点。FLPs 8a,b与二氧化碳反应生成双硼键合的加成产物。8b与共轭炔酮的反应通过在偕二FLP骨架处炔烃的反式1,2 - 氢膦化正式进行，得到七元杂环21。
