89332-64-9Relevant academic research and scientific papers
Addition, Substitution, and Deoxygenation Reactions of α-Phenyl-β-nitrostyrenes with the Anions of Thiols and Diethyl Phosphite: Formation of Indoles by Reaction with Ethyl Phosphites
Russell, Glen A.,Yao, Ching-Fa,Tashtoush, Hasan I.,Russell, June E.,Dedolph, Douglas F.
, p. 663 - 669 (2007/10/02)
Reaction of excess RS- (R=Ph, t-Bu) with Ph2C=C(SPh)NO2 in Me2SO form Ph2C=CHSR via conversion of the initial Michael-type adducts into Ph2C(SR)CH=NO2- and Ph2C=CHNO2.In a similar fashion, reaction of (EtO)2PO- with Ph2C=C(SPh)NO2 forms initially mainly PhSP(O)(OEt)2 and Ph2CCH=NO2-, which upon acidic workup will yield the nitroalkane or the Nef reaction product, Ph2CCHO.The reaction of (EtO)2PO- with Ph2C=C(SPh)NO2 also produces Ph2CCN via a Perkow-type reaction of the Michael adduct to yield Ph2CCH=N(O)OP(O)(OEt)2 as an intermediate.The nitrile is also formed from Ph2CCH(NO2)2 with (EtO)2PO- in (EtO)2P(O)H or Me2SO at 30 deg C and in >95percent yield by the reaction of (EtO)3P with Ph2CCH(NO2)2 at 150 deg C.Reaction of Ph2C=CHNO2 or Ph2CCH2NO2 with excess (EtO)PO- in Me2SO or (EtO)2P(O)H forms 3-(diethoxyphosphinyl)-2,2-diphenylaziridine by a process postulated to involve Ph2C=CHN(O-)OP(O)(OEt)2, Ph2C=CHNOP(O)(OEt)2-, and 2,2-diphenyl-2H-azirine.Similarly, Ph2C=C(SBu-t)NO2 and (EtO)2PO- give 3-(tert-butylthio)-2,2-diphenyl-2H-azirine in Me2SO or 2-(tert-butylthio)-3-phenylindole in (EtO)2P(O)H solution.Deoxygenation of Ph2C=C(X)NO2 to form the 2-X-3-phenylindoles occurs in high yield at 150 deg C in (EtO)3P with X=H, PhS, or t-BuS while 2-nitrro-3-phenylindole is formed from Ph2C=C(NO2)2 in (EtO)2P(O)H at 150 deg C.
ACTIVATION OF CARBOXYL GROUPS BY DIPHENYL 2-OXO-3-OXAZOLINYLPHOSPHONATE. FACILE PREPARATION OF VERSATILE REAGENTS, 3-ACYL-2-OXAZOLONES
Kunieda, Takehisa,Higuchi, Tsunehiko,Abe, Yoshihiro,Hirobe, Masaaki
, p. 3253 - 3260 (2007/10/02)
Synthetic utility of the 2-oxazolone moiety as an excellent new leaving group is described.Based on such a function of the heterocycles, diphenyl 2-oxo-3-oxazolinylphosphonate has been newly introduced as a carboxyl-activating reagent which permits a facile direct preparation of 3-acyl-2-oxazolones and amides including peptides from a wide variety of carboxylic acids.The 3-acyl-2-oxazolides also serve as versatile reactive agents for highly chemoselective acyl-transfer to the nucleophilic species such as amines, alcohols and thiols, providing convenient and high-yield routes to amides, esters and thiol esters under mild conditions.They are also useful intermediates for ketones and alcohols.
EFFICIENT CONVERSION OF CARBOXYLIC ACIDS INTO THIOL ESTERS
Kunieda, Takehisa,Abe, Yoshihiro,Hirobe, Masaaki
, p. 1427 - 1428 (2007/10/02)
A facile and direct preparation of thiol esters from carboxylic acids and thiols using diphenyl 2-oxo-3-oxazolinylphosphonate in the presence of triethylamine is described.
