Ligand coupling reaction on the phosphorus atom

Reactions of heteroaryllithium compounds with phosphorus trichloride, phosphorus oxychloride, and thionyl chloride. Formation of heterocyclic biaryls

“…pyridyl in the reaction with 2-benzothiazyllithium or 2-pyridyllithium, respectively [ 1,3]. A similar coupling was also found in the reactions of phosphine oxides bearing two or three pyridyl groups with organometallic reagents [3,4]. Also, many 2pyridyl sulfoxides have been found to undergo ligand coupling by treatment with a Grignard reagent [5,6] or an organolithium reagent [6,7].…”

“…After the reaction mixture had been stirred for 2 hours at -4O"C, a solution of phosphorus trichloride (1.72 g, 12.5 mmol) in diethyl ether (50 mL) was slowly added at -40°C. The reaction mixture was stirred for 2 hours, warmed to room temper-Phosphoms Trichlori 2 e 1) 4 n-BuLI 1) 3 n-BuLI 1) 4 n-BuLI 1) 3 n-BuLI 2) SOCI, 4 WBr 2, -m-N' / Et20, a B r -40°C, Ar Et20r 1g -4OoC, Ar 2g SCHEME 2 ature, and then mixed with water (100 mL). The solid product was separated from the solution by filtration, washed with water, and dried.…”

Quantum chemical studies on acidity-basicity behaviors of some bipyridine derivatives

“…It seems that the substituted bipyridine derivatives have been prepared mostly by reactions of Grignard reagents or organo-lithium derivatives with various sulfur and phosphor containing compounds respectively. [1][2][3][4][5][6][7][8][9] Studies on structure of bipyridine derivatives are also indicate an enormous amount of research affords. A low temperature X-ray structure, 10 the theoretical calculations [11][12][13][14][15] and spectroscopic studies of bipyridine derivatives have been reported in the literature.…”

Round-Trip Oxidative Addition, Ligand Metathesis, and Reductive Elimination in a PIII/PV Synthetic Cycle

“…Recent excellent examples by McNally (for heteroaryl functionalization via a P V →P III RE step) and Cornella (for functionalization of aryl boron compounds via a Bi V →Bi III RE step) are paradigmatic; nonetheless, the high-valent aryl­pnictogen­(V) intermediates are accessed via the use of an exogenous oxidant (S VI reagent in the former, “F + ” reagent in the latter), not aryl C–X OA. Indeed, while both OA − and RE , are independently known within the P III /P V couple, no single system exhibits the full suite of elementary steps in the aryl C–X substitution mechanism. Here, we report well-defined stoichio­metric reactions atop a single phosphorus platform that trace a closed P III /P V synthetic loop comprising aryl C–F OA and aryl C–H RE interposed with F→H ligand metathesis (Figure B) .…”