Journal of Organometallic Chemistry
Volume 560, Issues 1-2, 15 June 1998, Pages 253-255
Reductive dimerization of dialkyl acetylenedicarboxylate catalyzed by [Rh(binap)(MeOH)2]ClO4 in methanol
This article is not included in your organization's subscription. However, you may be able to access this article under your organization's agreement with Elvier.
Kazuhide Tani*, Kazuya Ueda, Kenji Arimitsu, Tsuneaki Yamagata and Yasutaka Kataoka
Department of Chemistry, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka, 560-8531, Japan
感恩节火鸡Received 16 January 1998;
revid 10 February 1998.
Available online 6 July 1998.
Abstract
止嗽立效丸
Cationic Rh(I) complex [Rh(binap)(MeOH)2]ClO4 catalyzes reductive dimerization of dialkyl acetylenedicarboxylates 1骨是多音字吗 to give 1,2,3,4-tetrakis(alkoxycarbonyl)-1,3-butadienes 2 in methanol lectively.
Author Keywords: Dimerization; Cationic; Rhodium
Article Outline
Acknowledgements
References
J. Chem. Soc., Chem. Commun., 1982, 600 - 601, DOI: 10.1039/C39820000600
Cationic rhodium(I春节对联赏析) complex-catalyd asymmetric isomerisation of allylamines to optically active enamines
Kazuhide Tani, Tsuneaki Yamagata, Sei Otsuka, Susumu Akutagawa, Hidenori Kumobayashi, Takanao Taketomi, Hidemasa Takaya, Akira Miyashita and Ryoji Noyori
The cationic rhodium(I) complex(+)- or (–)-2,2bis(diphenylphosphino)-1,1-binaphthyl(cyclo-octa-1,5-diene)rhodium perchlorate, effectively catalys the isomersiation of N,N-diethylnerylamine or N,N-diethylgeranylamine to produce optically active N,N-diethylcitronellal-(E)-enamine with excellent enantiolectivity (> ca. 95% enantiomeric excess) and chemolectivity (> ca. 98%).
-----------------
. Chem. Soc., Chem. Commun., 1988, 466 - 468, DOI: 10.1039/C39880000466
A new rhodium trinuclear complex containing highly protected hydroxo groups, [{Rh(binap)}3(µ3-OH)2]CIO4, responsible for deactivation of the 1,3-hydrogen migration catalyst of allylamine [binap = 2,2-bis(diphenylphosphino)-1,1-binaphthyl]
Tsuneaki Yamagata, Kazuhide Tani, Yoshitaka Tatsuno and Taro Saito
A new stable rhodium trinuclear complex, [{Rh(binap)}3(µ3-OH)2]ClO4[binap = 2,2-bis(diphenylphosphino)-1,1-binaphthyl](2), formed when water deactivates the RhI–binap complex catalyd asymmetric 1,3-hydrogen migration of allylamine, has been isolated; and X-ray structural analysis of the deuterium derivative [{Rh[(+) binap]}3(µ3关于历史的电影-OD)2]ClO4 revealed a unique structure with two highly protected µ3-hydroxo groups.
-------------------
A new rhodium trinuclear complex containing highly protected hydroxo groups, [{Rh(binap)}3(μ3-OH)2]ClO4, responsible for deactivation of the 1,3-hydrogen migration catalyst of allylamine [binap = 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl] [Erratum to document cited in CA109(8):65839u].
Journal of the Chemical Society, Chemical Communications (1989), (1), 67. CODEN:JCCCAT ISSN:0022-4936.
Article
Axially Dissymmetric Bis(triaryl)phosphines in the Biphenyl ries: Synthesis of (6,6-dimethylbiphenyl-2,2-diyl)bis(diphenylphosphine) (BIPHEMP) and analogues, and their u in Rh(I)-catalyzed asymmetric isomerizations of N,N-diethylnerylamine |
Rudolf Schmid *, Marco Cereghetti, Bernd Heir, Peter Schönholzer, Hans-Jürgen Hann |
Zentrale Forschunginheiten, F. Hoffmann-La Roche & Co. AG, CH-4002 Bal |
|
*Correspondence to Rudolf Schmid, Zentrale Forschunginheiten, F. Hoffmann-La Roche & Co. AG, CH-4002 Bal
The axially dissymmetric diphosphines (-)-(R)- and (+)-(S)-(6-6-dimethylbiphenyl-2,2-diyl)bis(diphenyl-phosphine) ((-)-(R)-10 and (+)-(S)-10; BIPHEMP) have been synthesized, starting from (R)- and (信托产品怎么买S)-6,6-dimethylbiphenyl-2,2-diamine ((R)- and(S)-卫生间标语16), respectively, via Sandmeyer reaction, liathiation, and phosphinylation. Moreover, racemic 4,4- dimethyl- and 4,4-bis(dimethylamino)-substituted analogues 11 and 12 respectively, and the 6,6-bridged analogues 1,11-bis(diphenylphosphino)-5,7-dihydrodibenz[c,e]oxepin (13) were synthesized and resolved into optically pure (R)- and(S)-enantiomers via complexation with di--chlorob is {(R)-2-[1-(dimethylamino)ethyl]pheny-CN}dipalladium(II) ((R)-18). The molecular structures of the diphosphines (S)-10 and (R)-13 and of two derived cationic Rh(I) complexes,[Rh((S)- 10)(nbd)]BF4 and [Rh((R)- 13)(nbd)]BF4 were determined by x-ray analys. Absolute configurations were established for (+)-(S)- 10 by X-ray analys of both the free diphosphine and of the derived Rh(I) complex, and for (-)-(R)- 13 by X-ray analysis of the derived Rh(I) complex. Configurational assignments for the substituted BIPHEMP analogues 商洛景点11 12 were achieved by means of 1H-NMR comparisons. The BIPHEMP ligand 10 and analogues 11, 12 and 13 are the first examples of optically active bis(triaylphosphines) containing the axially dissymmetric biphenyl moiety. All the new diphosphines proved to be excellent asymmetry-inducing ligands in Rh(I)-catalyzed isomerizations of N,N-diethylnerylamine affording citronellat enamine of 98-99% ee. |
|
