Desymmetrization of meso-Diols by Acylation with Axially Chiral Twisted Amides and Its Mechanistic Studies

Yamada, Shinji; Katsumata, Hiroko

doi:10.1246/cl.1998.995

Cited by 16 publications

(3 citation statements)

References 12 publications

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“…67–69 The effect of amide distortion has been leveraged to control chemical transformations 132–140 including hydrolysis, 61–66 acylation, 132–134 desymmetrization 135 and kinetic resolution 136,137 of alcohols. Bridged lactams have been applied as intermediates in the synthesis of bioactive natural products 141–192 and are even present in the structures of several alkaloids.…”

Section: General Properties Of Bridged Lactamsmentioning

confidence: 99%

“…Nonplanar amides have been frequently employed to investigate fundamental properties of amide bonds, such as proton exchange, − bonding, − rotational barriers, , and chemical reactivity. − The effect of amide distortion has been leveraged to control chemical transformations − including hydrolysis, − acylation, − desymmetrization, and kinetic resolution , of alcohols. Bridged lactams have been applied as intermediates in the synthesis of bioactive natural products − and are even present in the structures of several alkaloids. − …”

Section: General Properties Of Bridged Lactamsmentioning

confidence: 99%

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Chemistry of Bridged Lactams and Related Heterocycles

2013

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CONTENTS 1. Introduction 5702 2. General Properties of Bridged Lactams 5703 2.1. Distortion Parameters of Bridged Lactams 5703 2.2. Bond Lengths of Bridged Lactams 5703 2.3. Spectroscopic Properties of Bridged Lactams 5703 2.4. Analogy of Bridged Lactams to Bridgehead Olefins 5704 2.5. Chemical and Biological Significance of Distorted Amides 5704 3. Synthesis of Historically Important Bridged Lactams 5704 3.1. Quinuclidone Derivatives 5704 3.2. Adamantanone Derivatives 5707 4. Synthesis of Bridged Lactams with the N−(CO) Bond on a Two-Carbon or Larger Bridge, ([m. (≥2).n] Type) 5708 4.1. Condensation Reactions Forming the N− C(O) Bond 5708 4.2. Heck Reactions 5711 4.3. Diels−Alder Reactions 5712 4.4. Carbene Insertion Reactions 5713 4.5. Reactions via Radical Intermediates 5714 4.6. Miscellaneous Examples 5714 5. Synthesis of Bridged Lactams with the N−(CO) Bond on a One-Carbon Bridge, ([m.1.n] Type) 5715 5.1. Carbene Insertion Reactions 5715 5.2. Schmidt Reactions 5716 5.3.

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Section: General Properties Of Bridged Lactamsmentioning

confidence: 99%

Section: General Properties Of Bridged Lactamsmentioning

confidence: 99%

Chemistry of Bridged Lactams and Related Heterocycles

2013

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“…An intensive effort has been made to develop enantioselective acylation catalysts, and much progress has been recorded in the kinetic resolution of secondary alcohols . The desymmetrization of diols has also been explored, − and promising methodology has been reported using heavy metal-free catalytic conditions. − So far, the most widely applicable catalyst appears to be Oriyama's diamine 1 . This catalyst promotes the desymmetrization of aliphatic meso -diols with exceptional selectivity at −78 °C, as illustrated for the conversion of 2 to 3 (96% ee).…”

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Desymmetrization of meso-Hydrobenzoin Using Chiral, Nucleophilic Phosphine Catalysts

2004

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The desymmetrization of meso-hydrobenzoin is described using chiral phosphine catalysts 8b-d and 9-11. The best enantioselectivity at room temperature was obtained with the newly synthesized phospholane 8c and benzoic anhydride, but the reaction is very slow. Much faster reactions, but somewhat lower enantioselectivities were observed using the bicyclic phosphine catalyst 9. To obtain product 5a with >90% ee required conditions where the ee is upgraded due to the formation of the dibenzoate 6a. Among the new phospholane catalysts, 8b has the best selectivity in the kinetic resolution of benzylic alcohols, but not at the level observed previously with catalyst 11.

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Kinetic Resolution and Desymmetrization of Alcohols and Amines by Nonenzymatic, Enantioselective Acylation

et al. 2020

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Enantiomerically pure alcohols and amines are ubiquitous throughout Nature and are found within numerous biologically active compounds. This chapter provides a comprehensive overview of strategies for the nonenzymatic acylative kinetic resolution and desymmetrization of alcohols and amines, which have emerged as powerful methods for the preparation of a range of enantiomerically enriched alcohol and amine derivatives. The use of both stoichiometric chiral acylating agents and the use of small‐molecule catalysts for such processes is discussed. The chapter provides an overview of the variety of substrates that can be effectively resolved using the range of enantioselective acylation methods available. Key mechanistic considerations within each class of acylation and the origin of stereoselectivity are also discussed.

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Desymmetrization of meso-Diols by Acylation with Axially Chiral Twisted Amides and Its Mechanistic Studies

Cited by 16 publications

References 12 publications

Chemistry of Bridged Lactams and Related Heterocycles

Chemistry of Bridged Lactams and Related Heterocycles

Desymmetrization of meso-Hydrobenzoin Using Chiral, Nucleophilic Phosphine Catalysts

Kinetic Resolution and Desymmetrization of Alcohols and Amines by Nonenzymatic, Enantioselective Acylation

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