Phospholane sulfides

Diethylamino-3-phenyl- E2, 639 2-Diethylamino-3-phenyl- -2-oxid E2, 639 2-Diethylamino-3-phcnyl- -2-sulfid XII/2, 776f. aus 2-Diethylamino-3-phenyl-1,3,2-oxaza-phospholan und Scliwefel XII/2, 782 2-Dimethylamino-3-methyl- E2, 840 2-Dimethylamino-3-phenyl- -2-sulfid XII/2, 777... 

The 1,1-dihalides are rarely isolated but instead are hydrolysed to the 1-oxides,40-45 the position of the double bond being apparently unaltered thereby.39 The 1-sulfides can be obtained from (1) or (2) by means of H2S,46 and the phospholenes themselves by reduction with Mg or LiAlH4.47 Hydrogenation of the phospholene 1-oxides over Raney nickel leads to the saturated phospholane 1-oxides.48... 

Phospholane derivatives were obtained by a diastereoselective approach. In the first step benzothiadiphosphole was reacted with an unsymmetrical bis-Grignard reagent. In the second step, the pentavalent, pentacoordinated phosphorus intermediate so obtained was reacted with a mono-Grignard reagent to afford another intermediate with a hexacoordinate phosphorus atom whose collapse resulted in the phospholanes isolated as sulfides. The starting materials and the products are outlined in Scheme 3. ... 

The enantioselective deprotonation of 128 and oxidative addition of the carbanion with Cu(II) afforded TangPhos disulfide as a mixture of diaster-eomers where the chiral C2-symmetric product was the major compound (66% de, 95% ee). A single recrystallisation afforded the desired optically pure TangPhos sulfide in 20% yield. The desulfuration was performed with hexa-chlorodisilane to yield the very air-sensitive Tangphos diphosphine in 88% yield. The synthesis of a family of phospholane-oxazoline ligands started with the preparation of carboxylic acid 129 by the proeedure in 40% yield after recrystallisation. The crude product was obtained in relatively low optical... 

C9H17N2O3PS, Imidazole 2-hydroxy-4,4,5,5-tetramethyl-1,3,2-dioxa-phospholane 2-sulfide, 44B, 609... 

Ci8H2iiN03PS H2O, Tetramethylammonium cis-4,5-diphenyl-1, 3,2-dioxa-phospholane-2-sulfide-2-hydroxylate monohydrate, 45B, 748 Cl 8 25CI2CUNOP, (2-(Diphenylphosphinoyl)ethyl)diethylammonium di-chlorocuprate(I), 40B, 622... 

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