Research Progress of Asymmetric Synthesis of Optically Active P-Stereogenic Organophosphoryl Compounds by Chiral Induction
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Stereocenter
Asymmetric induction
New optically active 3,5-dinitrosalicyloxazolines, derived from 3,5-dinitrosalicylonitrile and the chiral aminodiols (1S,2S)-(+)-2-amino-1-phenyl- 1,3-propanediol, (2S)-(-)-2-amino-1,1,4,4-tetraphenyl- 1,4-butanediol and (2S)-(-)-2-aminol, 1-diphenyl-1,3-butanediol, were prepared and used as in situ catalysts for enantioselective cyclopropanation reactions.
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C–H functionalization has been established as an efficient way to generate molecular complexity. The formation of stereogenic carbon atoms by asymmetric C–H functionalization has seen tremendous progress over the past decade. More recently, the direct catalytic modification of C–H bonds has been powerfully applied to the formation of noncarbon stereogenic centers, which constitute a key design element of biologically active molecules and chiral ligands for asymmetric catalysis. This area was opened by a seminal report describing enantioselective C–H functionalization for the formation of a silicon stereocenter. It rapidly expanded with advances in the enantioselective formation of phosphorus(V) centers. Moreover, enantioselective routes to chiral sulfur atoms in the oxidation states IV (sulfoxides) and VI (sulfoximines) have been disclosed. Herein, we discuss methods of using selective functionalization of C–H bonds to generate a remote heteroatom stereogenic center via an inner-sphere C–H activation mechanism.
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This chapter describes briefly optically active sulfur-containing derivatives whose chirality results from the presence of a stereogenic sulfur atom with different valency and coordination numbers. Thus, it updates the more or less rich literature reports on the most common approaches that have made it possible to isolate them as optically active forms. Their recent synthetic applications are also illustrated.
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Abstract Enantioselective organocatalytic synthesis of tetrahydropyridines bearing a chiral tetrasubstituted carbon stereogenic center has been achieved. The spiro‐type monoaryl phosphine catalyst, ( R )‐SITCP, was found to promote the formal [4+2] cycloaddition of saccharin‐derived ketimines and α‐methyl allenoate to afford the corresponding six‐membered N‐heterocycles in high yields and excellent regioselectivities with up to 93% ee .
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Abstract The enantioselective synthesis of P ‐stereogenic chiral organophosphines under organocatalysis is a challenging research field, and reports that use this approach are rare. Herein, we have developed the enantioselective synthesis of P ‐stereogenic chiral oxazaphospholidines by using a bicyclic thiazole as the organocatalyst in the P–N and P–O bond‐forming reaction. The P ‐chiral products were prepared in high yields with moderate enantioselectivities. The base that was used in this process had a significant influence on the enantioselectivity of the reaction and in some cases led to the opposite configuration of the P ‐chiral center.
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This review covers literature on enantioselective synthesis of molecules with substituted quaternary carbon stereocenters from 1992 to 2002. In this overview, we will consider not only the construction of stereocenter itself by generation of carbon-carbon bond or heteroatom-carbon bond, but also other approachs which deal with the preparation of chiral compounds having this type of stereocenters, such as resolution or enantioselective desymmetrization. Keywords: Enantioselective, Oxygen-, Nitrogen- and Halogen, stereocenters, chiral compounds, desymmetrization
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Carbon fibers
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Asymmetric catalysis is one of the most attractive and efficient approaches toward synthesis of chiral enantioenriched compounds using achiral compounds as substrates and reagents. Compared with the well-established enantioselective preparation of carbon-stereogenic compounds, the corresponding preparation of silicon-stereogenic compounds is much less explored. In fact, most of the available methods rely on the use of stoichiometric amounts of chiral reagents, and much less progress has been made on catalytic enantioselective synthesis from achiral compounds. This review article mainly focuses on our recent achievements in this research area through the use of a synthetic strategy that employs transition-metal-catalyzed enantioselective desymmetrization reactions of prochiral tetraorganosilanes.
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Abstract The enantioselective construction of all‐carbon quaternary stereocenters is one of the most challenging fields in asymmetric synthesis. An asymmetric desymmetrization strategy offers an indirect and efficient method for the formation of all‐carbon stereocenters. An enantioselective formation of cyano‐bearing all‐carbon quaternary stereocenters in 1,2,3,4,‐tetrahydroquinolines and 2,3,4,5‐tetrahydro‐1H‐benzo[ b ]azepines by copper‐catalyzed desymmetric N‐arylation is demonstrated. The cyano group at the prochiral center plays a key role for the high enantioselectivity and works as an important functional group for further transformations. DFT studies provide a model which successfully accounts for the origin of enantioselectivity.
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Asymmetric carbon
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Abstract Asymmetric catalysis is one of the most attractive and efficient ways of synthesizing chiral enantioenriched compounds from achiral precursors. Compared with the well‐investigated enantioselective preparation of carbon‐stereogenic compounds, the corresponding preparation of silicon‐stereogenic compounds is much less established. In particular, the available methods typically rely on the use of stoichiometric amounts of chiral reagents, and little progress has been made on catalytic enantioselective synthesis using prochiral organosilanes until recently. This Focus Review highlights recent advances in the catalytic enantioselective preparation of silicon‐stereogenic organosilanes under transition‐metal catalysis through desymmetrization of prochiral organosilanes including diorganodihydrosilanes and tetraorganosilanes.
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