Mild partial deoxygenation of esters catalyzed by an oxazolinylborate-coordinated rhodium silylene
作者:Songchen Xu、Jeffery S. Boschen、Abhranil Biswas、Takeshi Kobayashi、Marek Pruski、Theresa L. Windus、Aaron D. Sadow
DOI:10.1039/c5dt02844b
日期:——
of organic carbonyl compounds with silanes to give hydrosilylation products or deoxygenation products. The pathway to these reactions is primarily influenced by the degree of substitution of the organosilane. Reactions with primary silanes give deoxygenation of esters to ethers, amides to amines, and ketones and aldehydes to hydrocarbons, whereas tertiary silanes react to give 1,2-hydrosilylation of
亲电,配位不饱和的铑配合物的硼酸联恶唑啉,恶唑啉配位亚甲硅烷基,和N-杂环卡宾供体支持[κ 3 -N,硅,C-值PhB(OX ME2)(OX ME2 SiHPh)进出口的Mes }铑(H)CO] [HB(C 6 F 5)3 ](2,Ox Me2 = 4,4-二甲基-2-恶唑啉; Im Mes = 1-mesitylimidazole)由中性铑甲硅烷基PhB(Ox Me2)2 Im Mes } RhH(SiH 2 Ph)CO(1)和B(C 6 F 5)3。在这种不寻常的恶唑啉配位亚甲硅烷基结构2是由一个未观察异构体的阳离子铑亚甲硅基物种的重排提议形式[值PhB(OX ME2)2林的Mes } RhH的(SiHPh)CO] [HB(C 6 ˚F 5)3 ]由H抽象生成。复杂2催化有机羰基化合物与硅烷的还原反应,生成氢化硅烷化产物或脱氧产物。这些反应的途径主要受有机硅烷取代度的影响。与伯硅