Diphenylphosphinoyl

Tanner et al. also used an aziridine carbinol (viz. 54) as chiral ligand in asymmetric addition of diethylzinc to hT-(diphenylphosphinoyl)imines (Scheme 41) [54]. 

Scheme 10.18 Additions of ZnEt2 to diphenylphosphinoyl imines with binaphthyl-thiophosphoramide ligand.

Asymmetric addition to ketimine in a reagent controlled manner has seldom been reported, even by 2008. When we investigated the potential for tbis asymmetric addition around 1992, there were no known examples. In 1990, Tomioka et al., reported the first asymmetric addition of alkyl lithium to N-p-methoxyphenyl aldo-imines in the presence ofa chiral (3-amino ether with 40-64% ee [8] (Scheme 1.11). In 1992, Katritzky reported the asymmetric addition of Et2Zn to in situ prepared N-acyl imine in the presence of a chiral (3-amino alcohol with 21-70% ee [15] (Scheme 1.12). In the same year, Soai et al., reported the asymmetric addition of dialkylzinc to diphenylphosphinoyl imines in the presence of chiral (3-amino alcohols with 85-87% ee [16] (Scheme 1.13). These three reports were, to the best of... 

In an attempt to estimate the value for the anomeric effect contributing to the axial preference for the diphenylphosphinoyl... 

Studies of n4 compounds possessing three P-C bonds are presented below. In addition to a diazaphospho1e oxide,174 the internal molecular motions of triphenylphosphine oxide have been analysed,173 and the anomeric interaction of a diphenylphosphinoyl-1,3-dithiane estimated.174 The structures of two sulphides have been examined,... 

The first experimental determination of a singlet-triplet energy gap (Mst) for an organic nitrenium ion was made for the 1,3-dimethylbenzotriazolium ion . A powerful ligand, 4,5-bis(diphenylphosphinoyl)-l,2,3-triazole, has been synthesized and found to possess two different modes of chelation <00ACIE3321>. 

Bell, A., Davidson, A.H., Earnshaw, C., Norrish, H.K., Torr, R.S., and Warren, S., fl-Diphenylphosphinoyl ketones (Ph2POCH2CH2COR) stable reagents for P-ketocarbanions, Chem. Commun., 988, 1978. 

Details of various routes to allylphosphine oxides (43) have been reported, and the subsequent synthesis of 1,3-dienes has been illustrated by many examples.37 Also described are stereochemical aspects of these diene syntheses and of subsequent Diels-Alder cycloaddition reactions.37 High regioselectivity is observed in migrations of the diphenylphosphinoyl group from unsymmetrical sites, as in (44), in that both products have a double bond exocydic to the cyclohexane ring.38... 

Acylhydrazines R1 CONF1NF1R2 (R1 = Ph or PhCH2 R2 = Bu, PhCH2 or Ph) are produced by the action of hydroxamic acids R ONHOH on the primary amines R2NH2 in the presence of tosyl chloride or 2-chloro-l-methylpyridinium chloride94. O-(Diphenylphosphinoyl)-A-arylhydroxylamines 77 (R = NO2, Ac, Tos or CN) react with A-methylaniline to afford the hydrazine derivatives 7895. 

The efficiencies of 0-(diphenylphosphinoyl)hydroxylamine and hydroxylamine-O-sulphonic acid as electrophilic aminating agents have been compared96. The conversion of... 

Chiral amines, ArCH(R)NH2, can be prepared by addition of a dialkylzinc to A-(diphenylphosphinoyl)imines, ArCH=N—P(=0)Ph2, using a suitable auxiliary, followed by acid hydrolysis to cleave the phosphorus moiety. A series of 2-azanorbornylmethanols (65) give ee% up to 92%, and they also induce some enantioselectivity in additions to benzaldehyde. A highly organized transition state with two zincs is proposed one coordinates the nitrogens of substrate and catalyst and the other coordinates the oxygens. 

Harger has studied the rearrangement of A-substituted N-phosphinoylhydroxylamines in the presence of base . He proposed a concerted mechanism based on the observed retention of the configuration at the phosphorous center during the transposition , and on studies with 0-labelled compounds . Similar cyclic transition states 572 were proposed in the base-induced rearrangement of A,0-bis(diphenylphosphinoyl)hydroxylamines (571) (equation 254). However, in the rearrangement of O-benzoyl-A-(diphenylphosphino-thiol)hydroxylamine where a transposition of O and S atoms occurs, the proposed cyclic transition state has sulfur participation . 

The largest number of hydrogen bonds in crystal structures of alkyl hydroperoxides refer to intermolecular bonds between the hydroperoxide proton and functionalities of the type 0=X, where X denotes a sulfur (e.g. 27), carbon (e.g. 30) or a phosphorous atom (e.g. 32, Figure 14, Table 7)93,108,115 geometry of [l,2-bis(diphenylphosphinoyl)ethane] bis(2,2-dihydroperoxypropane) (32) in the solid state is a rare example of a bifurcated hydrogen bond between an OOH donor and an 0=X proton acceptor. 

Horner-Emmons. The use of (diphenylphosphinoyl)fluoroacetonitrile (48) to introduce the amino group... 

The alkoxy-inside model was further adapted in order to rationahze the stereoselectivities of nitrile oxide cycloadditions to alkenes that possess other allylic substituents. In the reaction of a-chiral alkenes (124) or allylic diphe-nylphosphane oxides (161) (Table 6.7), it was suggested that the largest group (L, diphenylphosphinoyl substituent) was anti, the medium sized group (M, alkyl or alkoxy substituent) was on the inside and the smallest group (S, hydrogen) was... 

The residue was purified by silica gel chromatography (eluent n-hexane-ethyl acetate, 1 1) to give 2-[2-(diphenylphosphinoyl)phenyl]-7-isopropyl-6,7-dihydro-5//-l-pyrindine (307.9 mg, 88 %) as a colourless solid. 

R)-2-[2-(Diphenylphosphinoyl)phenyl]-7-isopropyl-6, 7-dihydro-5/7-l-pyrindine (307.0 mg, 0.70 mmol)... 

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