Amino phosphines, reactions

The amino interchange reaction is another method commonly used for preparing phosphinous amides [67] (Scheme 9). The low boiling points of di-methylamine and diethylamine allow their displacement from Ar,AT-dimethyl and AT,iV-diethyl phosphinous amides, respectively, by other less volatile amines, leading to new members of the same class. High reaction temperatures are nevertheless required. 

Addition of chlorine to tris(amino)phosphines has been used to prepare the dichlorophosphoranes (91), although the corresponding reaction of dialkylamino-(diphenyl)phosphines (92) gave less stable products.79 Analytical data, but no spectra, have been described for (91).79... 

The phosphoranes (81),64 (82),65 and (83),68 each containing a hydrogen ligand, have been prepared by the now standard procedure from amino-phosphines and amino-alcohols. A similar reaction of the amino-alcohol (84) gave oxazaphosphol-idine derivatives (85).6 7... 

Diphenyloxathiolan-5-ones (60) give good yields of the corresponding olefins when heated with tris(diethy amino)phosphine.471 This reaction is an example of a general type ... 

To our knowledge, the first examples of asymmetrically substituted monocyclic phosphoranes are 60 and 61, described by Moriarty et al.135 and involving the reaction of a substituted o-benzoquinone136,137 (Scheme 6) on an aminophosphine (59), itself obtained by alcoholysis of 58 with l-( — )-menthol. In contrast to the amino phosphine 53 (Scheme 5), 59 is a mixture of the diastereoisomers 59a and b, and its reaction with 3,5-di-tert-butyl-l,2-benzoquinone yields two diastereoisomeric phosphoranes, 60a and b. Finally, alcoholysis of the P(V)—NR2 bond138 in 60a and b leads to 61a and b or 62. 

Optically pure ligands on Pd in allylic alkylation can give good enantiomeric excess. You have already seen the first chiral amino-phosphine as the ligand in a chiral Heck reaction and it also gives excellent results in this example. It has to be said, however, that this is a very well behaved example and the next one is more impressive. 

The electropilic phosphinidine complex 29 can be generated in situ by the reaction of dichloro(diisopropyl-amino)phosphine with Collman s reagent. By trapping reactions with various alkynes, amine-substituted phosphirene complexes 30 are accessible (Equation 24) <2000T137>. 

Crosslinking with amino phosphines 188) can take place according to the following reaction mechanism... 

In contrast, LiAlH reduction of (Me3Si)jNPNSiMe3 followed by reaction workup in the presence of HjO (or D O) yields a bis(amino)phosphine product . 

New y-ethoxycarbonyl- and ot-amino-alkyl-hydroxyphosphinic acid derivatives (366) and (367) were conveniently prepared by Michael addition or Kabachnik-Fields reaction of a new precursor, benzyloxymethyl hydrogen-phosphinate (368), with a,p-unsaturated esters or imines (Scheme 94). " Phosphinic acid inhibitors (369) of Cathepsin C were synthesized by addition of methyl acrylate to the appropriate a-amino phosphinic acid and by... 

Thirupathi, N., Liu, X., Verkade John, G. Reactions of tris(amino)phosphines with arylsulfonyl azides product dependency on tris(amino)phosphine structure. Inorg. Chem. 2003, 42, 389-397. 

A number of non-routine reactions of halogenophosphines are worthy of note. The first aliphatic phosphenium cation featuring a phosphorus-sulfur bond (17) has been obtained by treatment of the chlorophosphine (18) with aluminium trichloride in dichloromethane solution. A new synthesis of acyclic chiral t-phosphines has been developed which employs selective, sequential alkylation of the chloro(amino) phosphines (19) by Grignard and organolithium reagents. The key intermediates (19) are readily prepared by the... 

The need for new classes of strong non-ionic, non-nucleophilic bases has led Palacios and co-workers to investigate ylide (101) and its polymer-supported analogue (102) in this capacity. It was found that ylides (101) and (102) acted as versatile bases for selective A -alkylation reactions of P-amino phosphine... 

It was shown that dipiperidyl sulphide is converted into tris(dimethyl-amino)phosphine sulphide on standing in HMPA overnight, and that the overall reaction of piperidyl-lithium with elemental sulphur may therefore be written ... 

A 31P NMR study of the reactions of phosphoryl halides and 4-(dimethyl-amino)phosphine (DMAP) shows the formation of (DMAP)POX2+, (DMAP)-P02X (X = Cl, Br), to give (DMAP)2P02+ and PX5 as final products.1180... 

A similar reaction with carbon tetrachloride has been observed with N-silylated amino-phosphines, but sublimation of the products gives the cyclo-diphosphazanes (13) as a mixture of cis- and frons-isomers. The cyclo-diphosphazane (13 R = Ph) could also be obtained by treatment of... 

E.s.r. spectra have also been used to study the photolysis of spin-labelled natural phosphates and charge-transfer reactions involving tris(dimethyl-amino)phosphine and triphenylmethylphosphonium salts. ... 

A review on the reaction of tervalent phosphorus acid derivatives with halogens has appeared. Alkylbis(diisopropyl-amino) phosphines (41) react with carbon tetrachloride or bromotrichloromethane to give the P-halogeno ylides (42) below 0 The ylides rearrange to the substituted phosphines (43)... 

The reactions of ferrocenylphosphines and tris(diethylamino)phosphine with iodine lead to the formation of iodotri(organo)phosphonium iodides. The related chlorophosphonium chloride obtained from the reaction of tris(dimethyl-amino)phosphine with phosgene has been used as a dehydrating agent for the preparation of A-protected amino-acid amides. ... 

A study of the reactions of (silylamino)phosphines (8) with organic halides includes an unusual N to C silyl migration (Scheme 2). Alkylation of amino-phosphines usually occurs on P a rare example of A-alkylation is found in the rigid system (9). ... 

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