Regioselective Addition of Stannylcyanocuprates to Acetylenic Ethers: A Chemical and Spectroscopic Study
作者:Jorge A. Cabezas、Allan C. Oehlschlager
DOI:10.1055/s-1994-25492
日期:——
The reactions of acetylenic ether 1 with higher order cuprates 2a, 2b and 2c were studied chemically and spectroscopically. Conditions were developed to efficiently and regioselectively prepare α- and β-stannylvinyl ethers. 1H and 13CNMR studies of these reactions suggest that in the presence of HMPA, higher order stannylcyanocuprate, (Bu3Sn)2Cu(CN)Li2, 2a, exists in equilibrium with Gilman cuprate, (Bu3Sn)2CuLi.
n-Octyl ethers are obtained by reacting n-octyl halides with preformed alkoxides, or better, prepared in situ from ROH and solid KOH. Reactions are performed without any solvent but in the presence of a catalytic amount of tetra-alkyl ammonium salt (Aliquat 336). Good yields (⩾92% for primary R) are obtained at moderate temperatures and with easy work-up; for t-C4H9O-, elimination is a side reaction
正辛基醚是通过反应得到的正辛基卤化物与醇盐预成型,或更好,制备原位从ROH和固体KOH。反应在没有任何溶剂的情况下,但是在催化量的四烷基铵盐(Aliquat 336)的存在下进行。在中等温度下且易于后处理,可获得良好的收率(初级R的⩾92%);对于tC 4 H 9 O-,消除是一个副反应,并且考察了温度和离去基团性质的影响,因此可以在tC 4 H 9 OC 8 H的范围内获得tC 4 H 9 OC 8 H 17(产率77%)。甲苯磺酸正辛酯在36°下20小时。
Oxyanionic substituent effect on the carbon-hydrogen insertion of carbenes. Reaction of alkoxides with dichlorocarbene and chlorophenylcarbene
作者:Toshiro Harada、Eiji Akiba、Akira Oku
DOI:10.1021/ja00347a042
日期:1983.5
Cambi, L., Atti della Reale Accademia dei Lincei. Serie 5: Rendiconti Classe di scienze fisiche, matematiche e naturali., 1964, vol. 23 I, p. 244 - 252