使用水作为化学计量的 H 或 D 原子供体的简单烯烃和炔烃的催化转移氢化的例子很少。我们发现二硼试剂使用钯催化剂有效地介导了 H 或 D 原子从水中直接转移到不饱和 CC 键上。该反应在环境温度下对多种烯烃和炔烃进行,硼酸是唯一的副产物。机理实验表明,该反应是通过从水中的氢原子转移生成 Pd 氢化物中间体而实现的。重要的是,还实现了从化学计量的 D2O 中完全掺入氘。
Zero valent iron complexes as base partners in frustrated Lewis pair chemistry
作者:Hendrik Tinnermann、Craig Fraser、Rowan D. Young
DOI:10.1039/d0dt03551c
日期:——
The prototypical iron(0) complex [Fe(CO)3(PMe3)2] (1) forms a frustratedLewispair (FLP) with B(C6F5)3 (BCF). In this FLP, the iron complex acts as the Lewisbase partner, and the borane as the Lewis acid partner. This FLP is able to cleave H–H, H–Cl, H–O and H–S bonds in H2, HCl, H2O and HSPh. The FLP 1/BCF is shown to catalyze the hydrogenation of alkenes under mild conditions, where terminal alkenes
The hydrogenation of styrenes by hydridocobalt tetracarbonyl
作者:Jerome A. Roth、Paul Wiseman、Lois Ruszala
DOI:10.1016/s0022-328x(00)86792-3
日期:1982.12
The rates of hydrogenation of several styrene derivatives by stoichiometric hydridocobalt tetracarbonyl [HCo(CO)4] were measured and compared. The relative rates are discussed in terms of conjugative and steric effects on the geminate radical pair mechanism. An improved method for determining HCo(CO)4 concentration is described.
A diboron‐mediated rhodium‐catalysed transferhydrogenation system using water as the hydrogen donor is developed. The new system features broad substrate scope, good functional group tolerance, and controllable chemoselectivity. This rhodium‐based catalytic system provides a new tool for transferhydrogenation.
Generation, entrapment and reactivity of long-lived organic carbocations and radical cations within a supramolecular assembly: Ca Y zeolite
作者:K. Pitchumani、P. H. Lakshminarasimhan、Nicolette Prevost、D. R. Corbin、V. Ramamurthy
DOI:10.1039/a607124d
日期:——
Diarylethenes spontaneously form the corresponding radical cations and
carbocations upon inclusion within activated Ca Y zeolite; oxygen plays an
important role in the generation of the radical cations.
二元酚在加入活化的 Ca Y 沸石后会自发形成相应的自由基阳离子和碳阳离子;氧在自由基阳离子的生成过程中起着重要作用。
Catalyst-free photo-reductions of aromatic olefins and carbonyl compounds
作者:Jieliang Wu、Boyu Yan、Jiangtao Meng、Enqin Yang、Xiushen Ye、Qiuli Yao
DOI:10.1039/d2ob01353c
日期:——
We describe herein a catalyst-free, traditional reductant-free strategy for the direct photoinduced hydrogenation or deuteration of aromatic olefins, ketones, and aldehydes with simple bases as the only additives. A broad range of substrates were demonstrated with high yields and deuterium incorporations. Mechanistic experiments indicate a radical mechanism.