Catalyst‐ and Solvent‐Free Hydrophosphorylation of Aldimines with Secondary Phosphine Chalcogenides: Synthesis of Tertiary α‐Aminophosphine Oxides, Sulfides and Selenides

Abstract

Secondary phosphine chalcogenides mildly (no catalysts and solvents, 20-65 °C, 0.25-65.5 h) react with aldimines to deliver the hitherto unknown α-aminophosphine oxides, sulfides and selenides in good to excellent yields.

Phospha-Mannich reactions of phosphinous acids R 2 P–OH and their derivatives

“…Conditions Yield,% SF, r.t., 0.5 h 78 [118] 2 SF, 55 C, 5.5 h 81 [118] SF, 65 C, 5 h 99 [118] 4 SF, 65 C, 5 h 87 [118] SF, 65 C, 16 h 67 [118] 6 SF, 55 C, 6.5 h 70 [118] SF, 65 C, 5 h 76 [118] 8 SF, 55 C, 4 h 86 [118] SF, 65 C, 7 h 82 [118] 10 SF, 55 C, 5 h 93 [118] SF, 65 C, 8.5 h 78 [118] 12 SF, 55 C, 11 h 90 [118] C7H8, r.t.reflux 81 [107] 14 Et2O, reflux, 0.5 h 88 [137,138] Et2O, reflux, 0.5 h 89 [137,138] 16…”

“…b Yield is not reported. [104,105] 2 -C6H6-C5H5N + 20 [106] 3 -C7H8, reflux, 2 h 78 [107] 4 -C7H8, reflux, 6 h 80 [107] 5 W SF, 100 °C, 10 min 89 [7,108] 6 W SF, 100 °C, 10 min 88 [7,108] 7 -SF, 80 °C, 10 min 89 [7,108] 8 CdI2 C6H6, 40 C, 1.5 h 52 [109] -C7H8, 60 °C, 2.5 h 88 [110] 9 -C6H6-C5H5N + 25 [106] 10 -C6H6-C5H5N + 20 [106] 11 -SF, 50 °C, 30 h 88 [111] 12 -SF, 50 °C, 30 h 92 [111] 13 -SF, r.t., 24 h 78 [111] 14 -SF, r.t., 24 h 92 [111] 15 -C6H6, 60 C, 0.5 h 73 [112] 16 -C7H8, reflux, 1 h 95 [113] 17 -Et2O, reflux, 20 h 75 [114] 18 -C7H8, 110 C, 30 min 82 [115] 19 -EtOH, reflux, 16 h 77 [116] 20 -EtOH, reflux, 16 h 81 [116] 21 -EtOH, reflux, 16 h 76 [116] 22 -EtOH, reflux, 16 h 82 [116] PTSA C6H6, reflux, 5 h 80** [117] 24 -SF, 65 C, 58 h [118] 25 -SF, r.t., 0.25 h 98 [118] 26 -SF, 65 C, 4.5 h [118] 27 -SF, 65 C, 20.5 h 60 [118] 28 -SF, 55 C, 5.5 h [118] 29 -SF, 65 C, 65.5 h 90 [118] 30 -EtOH, reflux, 25 h [119] 31 -EtOH, reflux, 25 h 62 [119] 32 -EtOH, reflux, 25 h [119] 33 -EtOH, reflux, 25 h 73 [119] 34 -EtOH, reflux, 25 h [119] 35 -CHCl3, r.t., 24 h 88 [120] 36 -CHCl...…”

“…Et2O, reflux, 0.5 h 70 [137,138] Et2O, reflux, 0.5 h 84 [137,138] 18 Et2O, reflux, 0.5 h 66 [137,138] Et2O, reflux, 0.5 h 61 [137,138] 20 SF, 65 C 85 [118] S 30…”

Hydrophosphorylation of C=O/N Bonds Using Organophosphine Oxides or Sulfides

“…[22] Recent studies have proposed the [2 + 2] transition state as the key rate-determining step (RDS) in the hydrophosphorylation of C=N bonds with phosphine chalcogenides. [23][24][25] Yet, only one mechanistic analysis of phosphine chalcogenide reactivity has been reported, in which the experimental evidence supported the stepwise pathway involving tautomerization and nucleophilic attack. The in-depth kinetic investigation was conducted using a primary phosphine sulfide (i-BuP(S)H 2 ) and a family of substituted aryl imines.…”

(Aminoalkyl)diphenylphosphine sulfides: synthesis and application as building blocks in the design of multidentate ligands for cytotoxic Pd(ii) complexes

“…However, the synthesis and properties of their aliphatic analogs featuring aminoalkyl substituents at the phosphorus atom are still largely untapped. [9][10][11][12][13] This report describes the facile synthetic procedures for (aminomethyl)-diphenylphosphine sulfide and its aryl-substituted analogs and their use as building blocks in the design of multidentate ligands for cytotoxic Pd(II) complexes.…”