1025-09-8Relevant articles and documents
Palladium-catalyzed Si-C bond-forming silylation of aryl iodides with hydrosilanes: An enhanced enantioselective synthesis of silicon-stereogenic silanes by desymmetrization
Chen, Li,Huang, Jiang-Bo,Xu, Zheng,Zheng, Zhan-Jiang,Yang, Ke-Fang,Cui, Yu-Ming,Cao, Jian,Xu, Li-Wen
, p. 67113 - 67117 (2016/08/02)
An enantioselective Pd-catalyzed silicon-carbon bond-forming silylation reaction of aryl iodides with hydrosilanes for the synthesis of silicon-stereogenic silanes has been developed, in which a systematic optimization of a TADDOL-derived monodentate phos
Synthesis of optically active tertiary silanes via Pd-catalyzed enantioselective arylation of secondary silanes
Kurihara, Yu,Nishikawa, Michihiro,Yamanoi, Yoshinori,Nishihara, Hiroshi
supporting information, p. 11564 - 11566 (2013/01/15)
We herein describe the development of an efficient enantioselective catalytic system that promotes the arylation of secondary silanes. Our method involves treatment of secondary silanes and aryl iodides with a Pd 2(dba)3-asymmetric p
Stereocontrolled synthesis of tertiary silanes via optically pure 1,3,2-oxazasilolidine derivatives
Oka, Natsuhisa,Nakamura, Masahiko,Soeda, Naomi,Wada, Takeshi
experimental part, p. 2171 - 2178 (2009/10/23)
Optically pure 1,3,2-oxazasilolidine derivatives were synthesized from a chiral 1,2-amino alcohol. These heterocyclic compounds containing a stereogenic silicon atom produced tertiary silanes with excellent optical purity through successive reactions with
A stereoselective approach to optically active bifunctional 1,3-dimethyl-1,3-diphenyldisiloxanes
Oishi, Motoi,Kawakami, Yusuke
, p. 549 - 551 (2008/02/12)
(Matrix presented) Functionalized disiloxanes have attracted much attention as versatile synthetic intermediates in the preparation of disiloxane-containing polymers. In this report, a highly stereoselective (98% inversion) halogenating cleavage reaction of the silicon-naphthyl bond to obtain optically active (S,S)-1,3-dimethyl-1,3-diphenyldisiloxanediol ((S,S):(R,S):(R,R) = 86:14:0) was demonstrated.
Asymmetric Synthesis of Organosilicon Compounds Using a C2 Chiral Auxiliary
Kobayashi, Kimiko,Kato, Takayuki,Unno, Masafumi,Masuda, Shinji
, p. 1393 - 1401 (2007/10/03)
Optically active silanes were synthesized by a novel asymmetric synthesis which involved the diastereoselective ring-opening reaction of 1,3-dioxa-2-silacycloheptanes bearing a C2 chiral auxiliary with Grignard reagents, followed by a lithium aluminum hydride (LiAlH4) reduction. (R)-Ethylmethylphenylsilane and (R)-methylphenylpropylsilane were derived in 93%ee and 98%ee, respectively. The preparation of the other optical silanes is also described. The maximum rotations of some of them have been determined by 1H NMR and/or capillary GC methods. A mechanism for a diastereoselective ring-opening reaction is proposed based on the stereochemical results.
Asymmetric Synthesis of Silicon Compounds Using Chiral 5,6-Dimethoxy-1,3,2-dioxasilacycloheptane Derivatives
Kobayashi, Kimiko,Kato, Takayuki,Masuda, Shinji
, p. 101 - 104 (2007/10/02)
Asymmetric synthesis of silicon compounds was achieved in high optical yield by the substitution reaction of some chiral 5,6-dimethoxy-1,3,2-dioxasilacycloheptane derivatives with organometallic reagents followed by lithium aluminium hydride reduction.The
CLEAVAGE OF SILICON- AND GERMANIUM-TRANSITION METAL BONDS. DEPENDENCE OF THE STEREOCHEMISTRY ON THE NATURE OF THE LIGANDS AND THE GEOMETRY OF COMPLEXES
Cerveau, Genevieve,Colomer, Ernesto,Corriu, Robert J. P.
, p. 33 - 52 (2007/10/02)
The cleavages of some new optically active complexes containing Co-Si (or -Ge), Mn-Si (or -Ge), Re-Ge and W-Ge bonds are described.Electrophiles cleave the Co-Si bond with good retention of configuration at silicon, while the Mn-Si bond is not cleaved und
NUCLEOPHYLIC SUBSTITUTIONS AT SILICON; EVIDENCE FOR ION-PAIR DISSOCIATION AS CONTROLLING FACTOR OF THE STEREOCHEMISTRY AND A SIMPLE MECHANISTIC PROPOSAL
Corriu, R. J. P.,Guerin, C.
, p. 2467 - 2472 (2007/10/02)
Stereochemical and kinetic data are reported for reactions between organolithiums or LiAlH4 and some chiral organosilanes.They rule out a mechanism involving complexation control, such as the SNi-Si process proposed by Sommer et al.Electrophylic assistance to cleavage of a Si-X bond does not control the stereochemistry, but acts as an additional factor which can facilitate the inversion by increasing the ability of the leaving group to depart.The results reveal the dominant influence of ion-pair dissociation, and thus of the electronic character of the nucleophile: the consequence of the use of either hard reagents with a localized negative charge, such as alkyllithiums, or softer reagents with a more delocalized negative charge, support this dependence.A simple mechanistic interpretation of the data is proposed, based on a description of nuclepohilic substitutions at silicon as a frontier orbital process.