104855-61-0Relevant articles and documents
Efficient and Selective Nickel-Catalyzed Addition of H-P(O) and H-S Bonds to Alkynes
Han, Li-Biao,Zhang, Chen,Yazawa, Hideaki,Shimada, Shigeru
, p. 5080 - 5081 (2004)
The cheap nickel catalysts are more reactive than the corresponding noble metal catalysts in the catalytic additions of a variety of P(O)-H bonds and an S-H bond to alkynes, affording regio- and stereoselectively both the Markovnikov and the anti-Markovnikov adducts, respectively, in high yields. A related five-coordinate hydrido nickel complex in the catalysis is successfully isolated, which can react readily with an alkyne to give the addition products. Copyright
Palladium-catalysed regioselective addition reaction of ethyl phenylphosphinate with terminal acetylenes: Ligand- and solvent-dependent regioselectivity
Kumar Nune, Satish,Tanaka, Masato
, p. 2858 - 2860 (2007)
Palladium-1,2-bis(diphenylphosphino)ethane complex catalyses regioselective Markovnikov addition of ethyl phenylphosphinate to terminal alkynes in toluene, while the use of tri-tert-butylphosphine as the ligand or ethanol as the solvent leads to regiosele
Transition metal-free and regioselective vinylation of phosphine oxides and: H -phosphinates with VBX reagents
Castoldi, Laura,Rajkiewicz, Adam A.,Olofsson, Berit
, p. 14389 - 14392 (2020/12/01)
A series of phosphine oxides and H-phosphinates were vinylated in the presence of the iodine(iii) reagents vinylbenziodoxolones (VBX), providing the corresponding alk-1-enyl phosphine oxides and alk-1-enyl phosphinates in good yields with complete chemo- and regioselectivity. The vinylation proceeds in open flask under mild and transition metal-free conditions.
Hydrophosphorylation of Alkynes Catalyzed by Palladium: Generality and Mechanism
Chen, Tieqiao,Zhao, Chang-Qiu,Han, Li-Biao
supporting information, p. 3139 - 3155 (2018/03/08)
We carried out a comprehensive study on the generality, scope, limitations, and mechanism of the palladium-catalyzed hydrophosphorylation of alkynes with P(O)-H compounds (i.e., H-phosphonates, H-phosphinates, secondary phosphine oxides, and hypophosphinic acid). For H-phosphonates, Pd/dppp was the best catalyst. Both aromatic and aliphatic alkynes, with a variety of functional groups, were applicable to produce the Markovnikov adducts in high yields with high regioselectivity. Aromatic alkynes showed higher reactivity than aliphatic alkynes. Terminal alkynes reacted faster than internal alkynes. Sterically crowded H-phosphonates disfavored the addition. For H-phosphinates and secondary phosphine oxides, Pd/dppe/Ph2P(O)OH was the catalyst of choice, which led to highly regioselective formation of the Markovnikov adducts. By using Pd(PPh3)4 as the catalyst, hypophosphinic acid added to terminal alkynes to give the corresponding Markovnikov adducts. Phosphinic acids, phosphonic acid, and its monoester were not applicable to this palladium-catalyzed hydrophosphorylation. Mechanistic studies showed that, with a terminal alkyne, (RO)2P(O)H reacted, like a Br?nsted acid, to selectively generate the α-alkenylpalladium intermediate via hydropalladation. On the other hand, Ph(RO)P(O)H and Ph2P(O)H gave a mixture of α- and β-alkenylpalladium complexes. In the presence of Ph2P(O)OH, hydropalladation with this acid took place first to selectively generate the α-alkenylpalladium intermediate. A subsequent ligand exchange with a P(O)H compound gave the phosphorylpalladium intermediate which produced the Markovnikov adduct via reductive elimination. Related intermediates in the catalytic cycle were isolated and characterized.
PROCESS FOR PREPARATION OF ALKENYLPHOSPHINE OXIDES OR ALKENYLPHOSPHINIC ACID ESTERS
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Page 10, (2008/06/13)
A novel process for preparation of alkenylphosphine oxides or alkenylphosphinic acid esters provided by which the objective compounds can be easily, safely and efficiently synthesized and easily separated and purified with little formation of by-products
Palladium-Catalysed Synthesis of Alkyl Alkenylmethyl- and Alkenylphenylphosphinates
Yuanyao Xu,Zhong Li
, p. 240 - 242 (2007/10/02)
Alkyl alkenylmethyl- and alkenylphenylphosphinates were synthesized stereospecifically by the palladium-catalysed reaction of a monoalkyl methane- or benzenephosphonite with an alkenyl bromide in the presence of triethylamine with moderate to good yields.
