247940-06-3Relevant articles and documents
Palladium-Catalyzed C-P(III) Bond Formation by Coupling ArBr/ArOTf with Acylphosphines
Chen, Xingyu,Wu, Hongyu,Yu, Rongrong,Zhu, Hong,Wang, Zhiqian
, p. 8987 - 8996 (2021/06/30)
Palladium-catalyzed C-P bond formation reaction of ArBr/ArOTf using acylphosphines as differential phosphination reagents is reported. The acylphosphines show practicable reactivity with ArBr and ArOTf as the phosphination reagents, though they are inert to the air and moisture. The reaction affords trivalent phosphines directly in good yields with a broad substrate scope and functional group tolerance. This reaction discloses the acylphosphines' capability as new phosphorus sources for the direct synthesis of trivalent phosphines.
Rhodium-Catalyzed PIII-Directed ortho-C?H Borylation of Arylphosphines
Wen, Jian,Wang, Dingyi,Qian, Jiasheng,Wang, Di,Zhu, Chendan,Zhao, Yue,Shi, Zhuangzhi
supporting information, p. 2078 - 2082 (2019/02/01)
Transition-metal-mediated metalation of an aromatic C?H bond that is adjacent to a tertiary phosphine group in arylphosphines via a four-membered chelate ring was first discovered in 1968. Herein, we overcome a long-standing problem with the ortho-C?H activation of arylphosphines in a catalytic fashion. In particular, we developed a rhodium-catalyzed ortho-selective C?H borylation of various commercially available arylphosphines with B2pin2 through PIII-chelation-assisted C?H activation. This discovery is suggestive of a generic platform that could enable the late-stage modification of readily accessible arylphosphines.
Chemoselective Reduction of Phosphine Oxides by 1,3-Diphenyl-Disiloxane
Buonomo, Joseph A.,Eiden, Carter G.,Aldrich, Courtney C.
supporting information, p. 14434 - 14438 (2017/10/23)
Reduction of phosphine oxides to the corresponding phosphines represents the most straightforward method to prepare these valuable reagents. However, existing methods to reduce phosphine oxides suffer from inadequate chemoselectivity due to the strength of the P=O bond and/or poor atom economy. Herein, we report the discovery of the most powerful chemoselective reductant for this transformation to date, 1,3-diphenyl-disiloxane (DPDS). Additive-free DPDS selectively reduces both secondary and tertiary phosphine oxides with retention of configuration even in the presence of aldehyde, nitro, ester, α,β-unsaturated carbonyls, azocarboxylates, and cyano functional groups. Arrhenius analysis indicates that the activation barrier for reduction by DPDS is significantly lower than any previously calculated silane reduction system. Inclusion of a catalytic Br?nsted acid further reduced the activation barrier and led to the first silane-mediated reduction of acyclic phosphine oxides at room temperature.