Phthalocyanine-catalyzed hydrophosphorylation of hydrazones and azines

Benzaldehyde, acetone, and N-Boc-piperidone phenylhydrazones, as well as azines derived from aromatic aldehydes and ketones, react with diethyl phosphite in the presence of [tetra(tert-butyl)phthalocyanine]aluminum chloride to give α-hydrazino phosphonates in high yields.     

Palladium-catalyzed hydrophosphorylation and hydrophosphinylation of cyclopropenes

Novel transition-metal-catalyzed addition of P-H entities across the cyclopropene double bond has been developed. This transformation allows for mild and efficient preparation of phosphorus-containing cyclopropanes in good yields and high degrees of diastereoselectivity.     

Method of ketone hydrophosphorylation

Russian Journal of General Chemistry -     

Catalytic hydrophosphorylation of alkyl- and acylhydrazones

N-Boc- and N-acylhydrazino phosphonates were obtained for the first time by hydrophosphorylation of the appropriate hydrazones of aliphatic and aromatic aldehydes and heterocyclic and aliphatic ketones in the presence of [tetra(tert-butyl)phthalocyanine]aluminum chloride as a catalyst.     

Catalytic hydrophosphorylation of dialkyl 2-allylmalonates

The reaction of dialkyl hydrogen phosphites and diphenylphosphine oxide with dialkyl 2-allylmalonates in the presence of [Pd(Ph₃P)₄] is studied. The addition of the hydrophosphoryl compounds to the multiple bond is established to proceed by the Markovnikov rule. The reaction is accompanied by the side process of malonate dealkoxycarbonylation whose contribution to the main process depends on the nature of the reagents.     

Benzoylhydrazones in catalytic hydrophosphorylation

Reactions of benzoylhydrazones derived from heterocyclic and aromatic aldehydes and aliphatic, heterocyclic, and aliphatic-aromatic ketones with diethyl phosphite in the presence of [tetra(tert-butyl)phthalocyanine]aluminum chloride afford α-benzoylhydrazino phosphonates in high yields.     

Palladium-catalyzed asymmetric hydrophosphorylation of norbornenes

[reaction: see text] By using Josiphos ligands, palladium-catalyzed hydrophosphorylation of norbornenes with hydrogen phosphonates proceeded efficiently to give the corresponding phosphonates in high enantioselectivities.     

Ni-catalyzed regiodivergent hydrophosphorylation of enynes

A regiodivergent hydrophosphorylation of enynes with phosphites has been developed using earth-abundant nickel catalyst. The manipulation of regioselectivity can be achieved by regulating the insertion order of alkyne bonds with (RO)₂P(O)–Ni–H or R₂P(O)O–Ni–H species, respectively. Under the Ni/Xantphos catalysis, 4,1-hydrophosphorylation is selectively obtained while the adding of acid can promote reactions towards 1,2-addition. By employing an additional Pd–H catalysis, 2,1-hydrophosphorylation is also an accessible task in one-pot reaction. Mechanistic studies and analysis have also been performed to interpret the origin of the regioselective regulation. This work highlights the arts in accessing different regioisomers by diverting common elementary reaction steps.     

过渡金属催化高选择性膦氢化反应

本文总结了过去几十年特别是近15年来过渡金属催化下各种含磷-氢键的膦氢化合物对炔烃的高选择性膦氢化反应,详尽叙述了其发现、发展和现状.自1996年来,过渡金属催化高选择性膦氢化反应研究工作发展迅速,各种高选择性膦氢化反应不断开发,目前已具有底物适用范围广、过渡金属催化剂活性高、反应选择性高、原子经济性高、以及能满足不同合成需求等优点,并逐步向反应条件温和化、金属催化剂简单化、无配体化、合成步骤简易化以及原料催化剂成本低价化方向发展.虽然如此,至今仍缺乏关于本研究全面的综述和介绍,希望本文可以弥补文献缺陷,对过渡金属催化高选择性膦氢化反应研究有个客观全面的介绍.过渡金属催化烯烃的不对称膦氢化反应合成碳手性或磷手性的光学活性有机磷化合物作为相关研究中的起步最晚的分支,本文也将作阶段小结.     

Catalytic and Noncatalytic Ammonolysis of Chloropentafluorobenzene

Ammonolysis of chloropentafluorobenzene both in the presence and in the absence of copper(I) salt results mainly in replacement of the para- and ortho-fluorine atoms with respect to chlorine rather than replacement of the chlorine atom. Ammonolysis of 4-chloro-2,3,5,6-tetrafluoroaniline and 2-chloro-3,4,5,6-tetrafluoroaniline in the absence of copper(I) salt yields exclusively the corresponding fluorine substitution products, whereas in the presence of copper(I) salt the chlorine atom is replaced. Successive ammonolysis of chloropentafluorobenzene in the presence of copper catalyst along these two paths was put into the basis of a new method for preparation of 2,3,5,6-tetrafluoro-1,4-phenylenediamine.     

Stereospecific α-methallylation of hydroxyaldehydes by silatropic ene cyclisation

We describe the thermal rearrangement of aldehydes bearing an α-(allyl- or crotylsilyl)oxy substituent. The transformations are best described mechanistically as intramolecular silatropic ene reactions based on stereoselectivity, kinetic and computed transition state data. The overall process constitutes a stereospecific (meth)allylation of α-hydroxyaldehydes, under neutral conditions, in which the hydroxyl protecting group is also the (meth)allylating agent.     

Catalytic and Noncatalytic Ammonolysis of Polyfluorinated 1,3-Dichlorobenzenes

Reactions of 1,3-dichlorotetrafluorobenzene and 1,3-dichloro-2,4,6-trifluorobenzene with aqueous ammonia in the presence and in the absence of copper(I) salt lead to fluorine replacement by amino group in the para and ortho positions with respect to the chlorine atom. Ammonolysis of the resulting chloropolyfluoroanilines in the absence of a catalyst involves replacement of fluorine atom in the meta position with respect to the amino group. In the presence of copper(I) salt, catalytic aminodechlorination occurs at the para and ortho positions with respect to the amino group introduced in the first stage.     

Catalytic hydrophosphorylation of semicarbazones, thiosemicarbazones, carbonohydrazones, and oxalyldihydrazones

Reaction of diethyl phosphite with semicarbazones, thiosemicarbazones, carbonohydrazones, and oxalyldihydrazones of aliphatic and carbocyclic ketones catalyzed by [tetra(tert-butyl)phthalocyanine]aluminum chloride resulted in hydrophosphorylation of the C=N bonds of hydrazones under study.     

Highly enantioselective synthesis of optically active hydroxyaldehydes using a chiral catalyst

Optically active hydroxyaldehydes arc synthesized in 88–94% e.e. by the catalytic enantioselective addition of dialkylzinc using N,N-dibutylnorephedrine.