132286-87-4Relevant academic research and scientific papers
Nickel(0)-Catalyzed Enantio- and Diastereoselective Synthesis of Benzoxasiloles: Ligand-Controlled Switching from Inter- to Intramolecular Aryl-Transfer Process
Kumar, Ravindra,Hoshimoto, Yoichi,Yabuki, Hayato,Ohashi, Masato,Ogoshi, Sensuke
, p. 11838 - 11845 (2015)
A highly enantioselective synthesis of 3-aryl-, vinyl-, and alkynyl-2,1-benzoxasiloles (up to 99.9% ee and 99% yield) was achieved via the sequential activation of an aldehyde and a silane by nickel(0). This strategy was applied to a simultaneous generation of carbon- and silicon-stereogenic centers with excellent selectivity (dr = 99:1) via diastereotopic aryl transfer. Initial mechanistic studies revealed the complete switching of an aryl-transfer process from an intermolecular (racemic synthesis in the presence of IPr) to an intramolecular (enantioselective synthesis using chiral NHC, L5) fashion. A plausible rationale for the switching of the aryl-transfer process is given by a preliminary DFT calculation, which suggests that the coordination of 1 to the nickel(0)/L5 fragment in an 2-arene:2-aldehyde fashion would be a key to the intramolecular process, while the formation of the corresponding intermediate is not possible in the presence of IPr. Owing to the chemically labile nature of its C-Si and O-Si bonds, enantioenriched benzoxasiloles are utilized for the synthesis of chiral building blocks and antihistaminic and anticholinergic drug molecules such as (R)-orphenadrine and (S)-neobenodine with no erosion of the enantiomeric excess.
Self-assembled heteroleptic chiral ligands, assymetric catalyst systems and methods
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Page/Page column 5, (2008/06/13)
A method of synthesizing a heteroleptic, multiple metal-containing metallocyclic catalyst, particularly suited for asymmetric catalysis, comprising combining a plurality of plural functional group-containing, monodentate ligands of complementary chirality
Asymmetric Catalysis Using Self-Assembled Chiral Bidentate P,P-Ligands
Takacs, James M.,Reddy, D. Sahadeva,Moteki, Shin A.,Wu, Di,Palencia, Hector
, p. 4494 - 4495 (2007/10/03)
A strategy is described for modular catalyst development based upon metal-directed self-assembly of bifunctional subunits around a structural metal to form a heteroleptic complex in which a second set of ligating groups are now suitably disposed to bind a
A new protected acyl protecting group for exocyclic amino functions of nucleobases
Dreef-Tromp,Hoogerhout,Van Der Marel,Van Boom
, p. 427 - 430 (2007/10/02)
2-(Tert-butyldiphenylsilyloxymethyl)benzoyl chloride (SiOMB-Cl) reacts with the per-O-trimethylsilylated d-nucleosides C,G and A to give, after removal of the Si(Me)3 groups and 5′-O-protection with 4,4′-dimethoxytrityl chloride (DMT-Cl), the corresponding N-SiOMB-5′-O-DMT derivates, the SiOMB groups of which can easily be removed by fluoride ion. The SiOMB protected nucleosides proved to be suitable building units for the preparation of DNA fragments in solution and on a solid support.
