4.2.8. Reductive Coupling 3109 5. Reaction of Aromatic Compounds 3110 5.1. Electrophilic Substitutions 3110 5.2. Radical Substitution 3111 5.3. Oxidative Coupling 3111 5.4. Photochemical Reactions 3111 6. Reaction of Carbonyl Compounds 3111 6.1. Nucleophilic Additions 3111 6.1.1. Allylation 3111 6.1.2. Propargylation 3120 6.1.3. Benzylation 3121 6.1.4. Arylation/Vinylation 3121 6.1.5. Alkynylation 3121 6.1.6. Alkylation 3121 6.1.7. Reformatsky-Type Reaction 3122 6.1.8. Direct Aldol Reaction 3122 6.1.9. Mukaiyama Aldol Reaction 3124 6.1.10. Hydrogen Cyanide Addition 3125 6.2. Pinacol Coupling 3126 6.3. Wittig Reactions 3126 7. Reaction of R,â-Unsaturated Carbonyl Compounds 3127

Organic Reactions in Aqueous Media with a Focus on Carbon−Carbon Bond Formations: A Decade Update

Chiral nitrogen-containing compounds are widely distributed in nature and include many biologically important molecules (Chart 1). In these compounds, the nitrogen-containing units are known to play important roles for their bioactivities. For the synthesis of these chiral nitrogen-containing building blocks, use of imines as electrophiles is the most promising and convenient route.1 While many approaches using chiral imines or chiral nucleophiles have been reported,1 these diastereoselective reactions have some disadvantages. First, the procedures to introduce chiral auxiliaries to substrates and to remove them after the diastereoselective reactions are often tedious. Second, more than stoichiometric amounts of chiral sources are needed to obtain chiral compounds according to these reactions. On the other hand, catalytic enantioselective reactions provide the most efficient methods for the synthesis of chiral compounds,2 because large quantities of chiral compounds are expected to be prepared using small amounts of chiral sources. While much progress has been made recently in catalytic enantioselective reactions of aldehydes and ketones such as aldol,3 allylation,4 Diels-Alder,5 cyanation reactions,6 reduction,1b,2b etc., progress in catalytic enantioselective reactions of imines is rather slow. There are some difficulties in performing catalytic enantioselective reactions of imines. For example, in the cases of chiral Lewis acid promoted asymmetric Shū Kobayashi was born in 1959 in Tokyo, Japan. He studied chemistry at the University of Tokyo and received his Ph.D. in 1988 (Professor T. Mukaiyama). After spending 11 years at Science University of Tokyo (SUT), he moved to Graduate School of Pharmaceutical Sciences, University of Tokyo, in 1998. His research interests include development of new synthetic methods, development of novel catalysts (especially chiral catalysts), organic synthesis in water, solid-phase organic synthesis, total synthesis of biologically interesting compounds, and organometallic chemistry. He received the first Springer Award in Organometallic Chemistry in 1997.

https://chemistry.mdma.ch/hiveboard/picproxie_docs/000499541-cr980414z.pdf

Catalytic enantioselective addition to imines.

Water-tolerant solid acid catalysts.

Lanthanide complexes in multifunctional asymmetric catalysis.

Catalytic Enantioselective Addition of Allylic Organometallic Reagents to Aldehydes and Ketones

Rare Earth Metal Trifluoromethanesulfonates as Water-Tolerant Lewis Acid Catalysts in Organic Synthesis

The Aldol Reaction of Silyl Enol Ethers with Aldehydes in Aqueous Media

https://www.thieme-connect.com/products/ejournals/pdf/10.1055/s-1994-22923.pdf

Scandium Trifluoromethanesulfonate. A Novel Catalyst for Friedel- Crafts Acylation.

Asymmetric Diels-Alder reactions catalyzed by chiral lanthanide(III) trifluoromethanesulfonates. Unique structure of the triflate and stereoselective synthesis of both enantiomers using a single chiral source and a choice of achiral ligands

A chiral scandium catalyst, prepared from scandium trifluoromethanesulfonate (Sc(OTf) 3 ), (R)-(+)1,1'-bi-2-naphthol, and a tertiary amine in dichloromethane, was quite effective in the enantioselective Diels-Alder reactions of acyl-1,3-oxazolidin-2-ones with dienes, and the corresponding Diels-Alder adducts were obtained in high yields with high diastereo- and enantioselectivities

Shū Kobayashi

Papers

Rare Earth Metal Trifluoromethanesulfonates as Water-Tolerant Lewis Acid Catalysts in Organic Synthesis

The Aldol Reaction of Silyl Enol Ethers with Aldehydes in Aqueous Media

Scandium Trifluoromethanesulfonate. A Novel Catalyst for Friedel- Crafts Acylation.

Asymmetric Diels-Alder reactions catalyzed by chiral lanthanide(III) trifluoromethanesulfonates. Unique structure of the triflate and stereoselective synthesis of both enantiomers using a single chiral source and a choice of achiral ligands

A Chiral Scandium Catalyst for Enantioselective Diels-Alder Reactions