I. G. Trostyanskaya

NICKEL- AND PALLADIUM-CATALYZED CROSS-COUPLING AS A ROUTE TO 1- AND 2-ALKOXY- OR DIALKYLAMINOVINYLPHOSPHONATES

1- and 2-alkoxy- or dialkylaminovinylphosphonates were synthesized using reactions of the corresponding vinylhalides with di- and triethylphosphites in the presence of catalytic amounts of Ni salts and Pd complexes. The best way for synthesis of 1-alkoxy or dialkylaminoderivatives is the Pd-catalyzed cross-coupling reaction with (EtO)2POH and the best way for 2-alkoxy- or dialkylaminovinylphosphonates is the Arbuzov reaction with (EtO)3P catalyzed by Ni salts.

Cross-coupling of E,E-1,4-diiodobuta-1,3-diene with nucleophiles catalyzed by Pd or Ni complexes: a new route to functionalized dienes

E,E-1,4-Diiodobuta-1,3-diene can enter into cross-coupling reactions with carbon- or other element-centered nucleophiles in the presence of Pd or Ni complexes as catalysts. Convenient procedures were developed for the stereoselective synthesis of E,E-1,4-dialkenylbuta-1,3-dienes, dienyl-1,4-bisphosphonates, E,E-1,4-bis(diphenylphosphino)buta-1,3-diene, E,E-1,4-diphenylbuta-1,3-diene, and E,E-1,4-bis(thiophenyl)buta-1,3-diene.

Hydrophosphination of alkoxyalkenes catalyzed by transition metal complexes

Diphenylphosphine adds to alkyl vinyl ethers in the presence of Ni(II) and Pd(II) complexes with a high regioselectivity, leading to exclusive formation of the corresponding Markownikoff adducts which were isolated as 1-alkoxyalkyl(diphenyl)phosphine oxides via oxidation with hydrogen peroxide.

Transition metal-catalyzed cross-coupling of 1,4-diiodobutadienes with thiols—A novel route to 1,4-bis(R-sulfanyl)buta-1,3-dienes

Cross-coupling of 1,4-diiodobuta-1,3-dienes with thiols in the presence of Pd, Ni, and Cu complexes gives 1,4-bis[aryl(alkyl)sulfanyl]buta-1,3-dienes in high yields.

Stoichiometric and catalytic activation of sp2 C−H bonds: molecular structure of Os3(μ-H)(μ3-nBuOC=CHPEt2)(CO)9 and catalytic properties of this and related Os and Ru clusters

Abstract The thermal reaction of nBuOCH=CHPEt2 with Os3(CO)12 gives a new osmium triangular cluster, Os3(μ-H)(μ3-nBuOC=CHPEt2)(CO)9 (1), which was isolated in 62% yield. The structure of 1 has been determined by X-ray diffraction ( P 1 ¯ , a = 12.914(3), b = 13.984(4), c = 16.375(4) A, α = 66.83(2), β = 77.82(2), γ = 77.97(2)°, Z = 4, dcalc = 2.552 g/cm3, R = 0.0399 for 6636 reflections). The μ3-nBuOC=CHPEt2 in 1 acts as a five-electron donor. It forms a σ-bond with one Os atom and coordinates the second and the third Os atoms of the cluster by its olefinic bond and the phosphorus atom, respectively. Both complex 1 and Os3(μ-H)(μ-CH=CHR)(CO)10 (R=nC6H13, Ph) catalyze the silylation of terminal olefins with Et3SiH to yield the corresponding trans-triethylvinylsilanes and alkanes in moderate yield even at ambient temperature. The proposed mechanism of olefin silylation catalyzed by triangular metal clusters involves the olefin C−H bond activation on the triangular cluster core and formation of an intermediate which has a structure similar to that of cluster 1.

Formation of a PIII−C(sp2) bond by addition of diphenyl(trimethylsilyl)phosphine to activated acetylenes

Diphenyl(trimethylsilyl)phosphine reacts with alkoxy(alkyl)acetylenes to give mixtures of addition products, (2-alkoxy-2-trimethylsilylalkenyl)diphenylphosphines and (2-alkoxyalkenyl)diphenylphosphines. The reaction is sensitive to the solvent; in MeCN, it gives only nonsilylated products. (1-Alkoxyethenyl)diphenylphosphines were obtained as the main products upon the reaction of Ph2PSiMe3 with terminal alkoxyalkynes, irrespective of the reaction conditions.