Bis 2-oxo-3-oxazolidinyl phosphinic Chloride

Alternate Names V,V-bis(2-oxo-3-oxazolidinyl)phosphordi-amidic chloride V,V-bis(2-oxo-3-oxazolidinyl)-phosphorodi-amidic chloride phosphoric acid bis(2-oxooxazolidide)-chloride BOP-Cl BOPDCl. 

Physical Data white powder, mp 195-198 C hygroscopic. Solubility slightly sol CH2CI2, MeCN, THF, DMF dec H2O. Form Supplied in white to off-white powder, typically 97% pure. Analysis of Reagent Purity IR (KBr) 1775 (C=0), 765 (P-Cl) cm .  

Purification the outcome of reactions can be greatly affected by the purity of the reagent commercial samples may require to be washed with cold water and recrystallized from MeCN prior to use.  

Handling, Storage, and Precautions store in a cool dry place under nitrogen to preclude contact with moisture and oxygen. Use only in a chemical fume hood. Wear suitable protective clothing and eye/face protection. Causes bums and is harmful if swallowed, inhaled, or absorbed through skin. 

The mechanism of these reactions is assumed to involve displacement of chloride by the carboxylate anion to give a phospho-rodiamidate (eq 4). Subsequent nucleophilic attack of an alcohol, amine, or a carboxylate anion affords phosphorodiamidic acid and esters, amides, and anhydrides, respectively (eq 5). 

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Cyclization of 1-carboxypentyl pipecolinate with bis(2-oxo-3-oxazolidinyl)phosphinic chloride in DMF in the presence of Htinig s base afforded 3-butylperhydropyrido[2,l-f][l,4]oxazine-l,4-dione <1996DEP4440193>. Cyclization of methyl 4-(alr-3,5-H-2-oxomorpholin-5-yl)butyrate in boiling toluene provided ar-4,9a-//-4-phenylper-hydropyrido[2,l-f][l,4]oxazine-3,6-dione <1995H(41)1931, 2000T233>. 

According to the latter approach, reducing sugars 128 were reacted with triethylammonium dimethyl boranophosphate in the presence of bis(2-oxo-3-oxazolidinyl)phosphinic chloride as condensing reagent, 3-nitro- 1,2,4-triazole as nucleophilic catalyst and A,A-diisopropyl-A-ethyl-amine to provide boranophosphate triester derivatives 129 as anomeric... 

C van der Auwera, MJO Anteunis. N,N-bis(2-oxo-3-oxazolidinyl) phosphinic chloride (BOP-C1) a superb reagent for coupling at and with iminoacid residues. Int J Pept Prot Res 29, 574, 1987. 

A similar mechanism to the previous ones was proposed by Deng, Shi and coworkers for the bis(2-oxo-3-oxazolidinyl)phosphinic chloride (BOP-Cl, 269) catalytic Beckmann rearrangement (equation 82). Addition of the Lewis acid zinc chloride improved the catalyst performance and amides were synthesized in excellent yields (92-99%). 

Another potential problem with DCC is that at the completion of the reaction some DCU remains in solution with the product, necessitating additional purification. Water-soluble carbodiimide derivatives such as l-Cyclohexyl-3-(2-morpholinoethyl)carbodiimide Metho-p-toluenesulffonate and l-Ethyl-3-(3 -dimethylaminopropyl)carbodiimide Hydrochloride (EDCI) obviate this problem, as they are removed by a simple extraction. Many newer coupling agents have been developed for peptide synthesis and other acylation reactions. These include Benzotriazol-l-yloxytris(dimethylamino)phosphonium Hexafluorophosphate (BOP)," 0-Benzotriazol-l-yl-N,N,N, N -tetramethyluronium Hexafluorophosphate (HBTU)," Bis(2-oxo-3-oxazolidinyl)phosphinic Chloride (BOP-Cl), and (1 //-1,2,3-benzotriazol-1 -yloxy)tris(pyrTolidino)phosphonium hexafluorophosphate (PyBOP). In addition to linear and polymeric amides, lactams of various ring sizes have been synthesized using these methods (eq 1)."... 

The problem of epimerization during carbodiimide-mediated coupling of amino acids can also be overcome by the use of an alternative coupling agent. Once such system that still employs HOBT as an additive involves the use of bis(2-oxo-3-oxazolidinyl)phosphinic chloride (BOP-Cl) and N-... 

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