I₂/TBHP Mediated Divergent C(sp²)‐P Cleavage of Allenylphosphine Oxides: Substituent‐Controlled Regioselectivity

Abstract

A highly regioselective C(sp 2 )-P(O) cleavage of allenylphosphine oxides mediated by I 2 / TBHP is achieved for the first time. The divergent pathway via cleavage of (Ph)CÀ P(O) or (allene)CÀ P (O) modulated by substituents, renders the formation of 4-iodo-2-phenyl-5H-1,2-oxa-phosphole 2oxide and α-iodoenone derivatives, respectively. A plausible mechanism through radical pathways, along with the cleavage of phenyl and diphenylphosphine oxide moieties, are verified by the trapping experiments and 18 O-isotopic labeling studies.

Disulfide Promoted C−P Bond Cleavage of Phosphoramide: “P” Surrogates to Synthesize Phosphonates and Phosphinates

“…These phenomena drew our attention, and we speculated that these side reactions could be a new route for the synthesis of phosphine organic compounds (Scheme 1B). C−P bond rupture and reconstruction has been an emerging topic because it provides an easy way to prepare value‐added products from low‐functionality molecule [21] . In this study, we developed an efficient method to cleave the C−P bond of phosphoramides for synthesizing phosphates and phosphinates.…”

“…CÀ P bond rupture and reconstruction has been an emerging topic because it provides an easy way to prepare value-added products from low-functionality molecule. [21] In this study, we developed an efficient method to cleave the CÀ P bond of phosphoramides for synthesizing phosphates and phosphinates.…”

Computational Design and Analysis of a Multi-epitope Against Influenza A virus

“…The flexible AD rich (one Alanine and one aspartic acid residues) linkers were used to join the selected epitopes. the multi-epitope were analysed with common on-line algorithms: NetCTL 1.2 (Kumar et al 2020 ), nHLApred (Jahangiri et al 2018 ),CTLPRED (Charoenkwan et al 2020 ),TAPPRED (Bidmeshki et al 2018 ),P-CLEAVAGE (Liu et al 2019 ) and IEDB (Dhanda et al 2019 ). This approach was followed for peptide arrangements of individual protein and then the most probable arrangements satisfying basic criteria was selected to be combined again in a longer polytope.…”

Metal-free C(aryl)–P bond cleavage: experimental and computational studies of the Michael addition/aryl migration of triarylphosphines to alkynyl esters

“…1 §§For selected reviews, see ref. 1–7. Among the reported examples of carbon–carbon (C–C) 2–4 and carbon–heteroatom (C–X) 1,5–7 bond cleavage reactions, carbon–phosphorus (C–P) bond cleavage reactions, 8–15 ¶¶For selected reports, see ref. 8–15. are one of the most important transformations because organophosphorus compounds are widely utilized as pharmaceuticals, 16 phosphine ligands, 17,18 organocatalysts, 19 and functional materials.…”

“…1–7. Among the reported examples of carbon–carbon (C–C) 2–4 and carbon–heteroatom (C–X) 1,5–7 bond cleavage reactions, carbon–phosphorus (C–P) bond cleavage reactions, 8–15 ¶¶For selected reports, see ref. 8–15. are one of the most important transformations because organophosphorus compounds are widely utilized as pharmaceuticals, 16 phosphine ligands, 17,18 organocatalysts, 19 and functional materials. 20 Therefore, C–P bond cleavage reactions have been developed using various approaches such as radicals produced using photolysis 8 or peroxides, 9 reduction using transition metal catalysts 10 and alkali metals, 11 and via P( v ) intermediates 12–15 (Scheme 1A).…”