0000000000433326
AUTHOR
Delia Bautista
Mercurated and Palladated Iminophosphoranes. Synthesis and Reactivity
Reaction of the iminophosphorane Ph3PNC6H4Me-4 (1a) with Hg(OAc)2 and LiCl gives the mercurated iminophosphorane [Hg{C6H3(NPPh3)-2-Me-5}Cl] (2). The latter reacts with NaBr to give [Hg{C6H3(NPPh3)-2-Me-5}Br] (3). 2 reacts with MeC6H4NCO-4 or CX2 (X = O, S) to give [Hg{C6H3(NCNC6H4Me-4‘)-2-Me-5}Cl] (4) or [Hg{C6H3{NCNC6H3(HgCl)-1‘-Me-5‘}-2-Me-5}Cl] (5), respectively. Iminophosphoranes Ph3PNC6H4R-4 (1b) react with Pd(OAc)2 to give the complexes [Pd{κ2-C,N-C6H4(PPh2NC6H4R-4‘)-2}(μ-OAc)]2 (R = Me (6a), MeO (6b)), in which the palladation takes place at one of the phenyl substituents of the PPh3 group. Complex 6b reacts with NaBr or tBuNC to give [Pd{κ2-C,N-C6H4(PPh2NC6H4OMe-4‘)-2}(μ-Br)]2 (7) o…
Mono- and di-nuclear complexes of ortho-palladated and -platinated 4,4′-dimethylazobenzene with bis(diphenylphosphino)methane. More data on transphobia
Abstract Complexes [Pd(κ2-R)(μ-Cl)]2 [κ2-R=κ2-C,N′-C6H3(NNC6H4Me-4′)-2-Me-5 (1)] and [Pd(κ1-R)Cl(κ1-dppm)(κ2-dppm)]TfO [dppm=bis(diphenylphosphino)methane (2)] have been used to prepare new palladium derivatives containing dppm. Thus, complex 1 reacts with one equivalent of dppm to afford [{Pd(κ2-R)Cl}2(μ-dppm)] (3) and with AgClO4 and dppm (1:2:2 molar ratios) to give [Pd(κ2-R)(κ2-dppm)]ClO4 (4·ClO4). The triflate salt of this complex (4·TfO) reacts with PPh3 to yield [Pd(κ1-R)(PPh3)(κ2-dppm)]TfO (5). Dinuclear complexes were obtained by reacting 2, (i) with [AuCl(PPh3)] or [AuCl(tht)] (tht=tetrahydrothiophene) (1:1, −60 °C) and (ii) with 1 (2:1) to give, respectively, [Pd(κ1-R)Cl(μ-dppm…
The Reaction of 4-Amino-2-oxazolines with Isocyanates and Isothiocyanates. Synthesis and X-Ray Structures of Polysubstituted 2-Imidazolidinones, 1,3-Oxazolidines and 1,3-Thiazolidines.
Abstract Reactions of 4-alkylamino-2-phenyl-2-oxazolines 1 with isocyanates and isothiocyanates provide unprecedented efficient and regioselective heterocycle–heterocycle transformations. Compounds 1 reacted rapidly with tosyl isocyanate yielding directly 3-alkyl-4-benzamido-1-tosyl-2-imidazolidinones 4 in almost quantitative yields. The corresponding ureido intermediates 2 were not isolable species. However, the reactions with non-sulfonylated isocyanates or isothiocyanates were slower, leading to the expected ureido and thioureido derivatives 5, which were easily and efficiently transformed to either polysubstituted 2-imino-1,3-oxazolidine or 2-imino-1,3-thiazolidine hydrochlorides 7, res…
Insertion of One, Two, and Three Molecules of Alkyne into the Pd−C Bond of Ortho-palladated Primary and Secondary Arylalkylamines
The ortho-metalated complex [Pd2{κ2(C,N)-C6H4CH2CH2NHMe-2}2(μ-Br)2] (1) can be prepared by refluxing a 1:1 mixture of Pd(OAc)2 and N-methylphenethylamine in acetonitrile, followed by addition of an excess of NaBr. Complex 1 reacts with PPh3 to give the mononuclear derivative [Pd{κ2(C,N)-C6H4CH2CH2NHMe-2}Br(PPh3)] (2). The cationic complex [Pd{κ2(C,N)-C6H4CH2CH2NHMe-2}(py)2]ClO4 (3) can be obtained by reacting 1 with AgClO4 and pyridine. The previously reported complex [Pd2{κ2(C,N)-C6H4CH2NHCH2Ph-2}2(μ-Br)2] (A) reacts with PhC≡CCO2R (R = Me, Et) to give the monoinserted derivatives [Pd2{κ2(C,N)-C(Ph)═C(CO2R)C6H4CH2NHCH2Ph-2}2(μ-Br)2] (R = Me (4a), Et (4b)). These dimers react with neutral l…