Hydrocarbon Activation. Synthesis of β-Cycloalkyl (Di)nitriles through Photosensitized Conjugate Radical Addition
作者:Anna Maria Cardarelli、Maurizio Fagnoni、Mariella Mella、Angelo Albini
DOI:10.1021/jo010400k
日期:2001.11.1
Photoinduced hydrogen abstraction from aliphatic cyclic hydrocarbons (C(5) to C(7), C(12), as well as adamantane) by triplet aromatic ketones in the presence of alpha,beta-unsaturated (di)nitriles offers a straightforward entry to the corresponding alkylated (di)nitriles via the alkyl radicals. Yields are moderate to good depending on the olefins structure (substitution in beta slows down the addition
Contrasting chemistry of diphenylcarbene and fluorenylidene in cyclohexane
作者:T.G. Savino、V.P. Senthilnathan、M.S. Platz
DOI:10.1016/s0040-4020(01)90595-2
日期:1986.1
The chemistry of diphenylcarbene and fluorenylidene in cyclohexane was investigated. An examination of the product distributions, radical scavenging experiments and isotopic fractionation established that diphenylcarbene reacts with cyclohexane predominantly, if not exclusively, through its triplet state whereas fluorenylidene exhibits substantial chemistry from its low lying singlet state in addition
Bis(tri-n-butylstannyl)benzopinacolate: Preparation and use as a mediator of intermolecular free radical reactions
作者:David J. Hart、Ramanarayanan Krishnamurthy、Lori M. Pook、Franklin L. Seely
DOI:10.1016/s0040-4039(00)61484-3
日期:1993.12
Bis(tri-n-butylstannyl)benzopinacolate (2) serves as a thermal source of tri-n-butylstannyl radicals and mediates intermolecular coupling of selected alkyl halides to O-benzylformaldoxime and electron deficient olefins. A free radical non-chain mechanism is proposed for these reactions.
Highly Efficient Alkylation to Ketones and Aldimines with Grignard Reagents Catalyzed by Zinc(II) Chloride
作者:Manabu Hatano、Shinji Suzuki、Kazuaki Ishihara
DOI:10.1021/ja0628405
日期:2006.8.1
efficient alkylation to ketones and aldimines with Grignardreagents in the presence of catalytic trialkylzinc(II) ate complexes derived from ZnCl2 (10 mol %) in situ was developed. This simple Zn(II)-catalyzed alkylation could minimize the well-known but serious problems with the use of only Grignardreagents, which leads to reduction and aldol side products, and the yield of desired alkylation products
在由 ZnCl2 (10 mol%) 衍生的催化三烷基锌 (II) 酸酯配合物的存在下,使用格氏试剂高效地烷基化为酮和醛亚胺。这种简单的 Zn(II) 催化烷基化可以最大限度地减少仅使用格氏试剂而导致还原和羟醛副产物的众所周知但严重的问题,并且可以提高所需烷基化产物的产率。
Synthesis and Application of 2,6-Bis(trifluoromethyl)-4-pyridyl Phosphanes: The Most Electron-Poor Aryl Phosphanes with Moderate Bulkiness
The poor will be rich: BFPy phosphanes (see scheme) mimic the electronic and steric characters of P(C6F5)3 and PPh3, respectively. These novel ligands showed a large ligand acceleration effect on Stille coupling, the Rh‐catalyzed 1,2‐addition of aryl boronic acid to unactivated ketones and the asymmetric arylation of N‐tosylimine using phenylboronic acid.
穷人将变得富有:BFPy膦(参见方案)分别模仿P(C 6 F 5)3和PPh 3的电子和位阻特征。这些新颖的配体对Stille偶联,Rh催化的1,2-芳基硼酸加成到未活化的酮上以及N-甲苯磺胺使用苯基硼酸的不对称芳基化表现出很大的配体促进作用。