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Scott E. Denmark, Edwin Vedejs (Beteiligte)

Lewis Base Catalysis in Organic Synthesis, 3 Teile


Herausgegeben von Vedejs, Edwin; Denmark, Scott E.
1. Auflage. 2016. 1488 S. 244 mm
Verlag/Jahr: WILEY-VCH 2016
ISBN: 3-527-33618-4 (3527336184)
Neue ISBN: 978-3-527-33618-0 (9783527336180)

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This three-volume set represents the first comprehensive coverage of the rapidly expanding field of Lewis base catalysis that has attracted enormous attention in recent years. Lewis base catalysis is a conceptually novel paradigm that encompasses an extremely wide variety of preparatively useful transformations and is particularly effective for enantioselectively constructing new stereogenic centers. As electron-pair donors, Lewis bases can influence the rate and stereochemical course of myriad synthetic organic reactions. The book presents the conceptual/mechanistic principles that underlie Lewis base catalysis, and then builds upon that foundation with a thorough presentation of many different reaction types. And last but not least, the editors, Prof. Edwin Vedejs and Prof. Scott E. Denmark, are without doubt the leaders in this emerging field and have compiled high quality contributions from an impressive collection of international experts.
Historical Introduction
PRINCIPLES
Definitions, terminology, and orbital treatment
Thermodynamic treatments of Lewis basicity
Kinetic treatments of Lewis basicity and nucleophilicity
MECHANISM AND LEWIS BASE CATALYSIS: NUCLEOPHILICITY IS ONLY PART OF THE STORY
Anhydride activation by 4-dialkylaminopyridines and analogs (n-pi )
LB catalysis vs. general base catalysis in enantioselective reactions
LB catalyzed-protic acid mediated reactions (n-pi )
Mechanistic options for the Morita-Baylis-Hillman reaction (n-pi )
Mechanism of C-Si cleavage using anionic Lewis base (n-sigma )
LB catalyzed - Lewis Acid mediated reactions (n-sigma )
Bifunctional LB catalysis with dual activation of R-M and C=O (n-sigma )
Bifunctional LB catalysis with dual activation of C=O and B H or B C (n-sigma )
APPLICATIONS: LEWIS BASE CATALYSIS INVOLVING AN n-pi ACTIVATION STEP
Acyl transfer catalyzed by Lewis bases
Morita-Baylis-Hilman reaction and vinylogous MBH
Beyond MBH
Iminium Catalysis
Enamine Catalysis
APPLICATIONS: ENHANCED NUCLEOPHILICITY BY LEWIS BASE ACTIVATION (n-pi ; n-sigma )
Si C-X and Si C-EWG as carbanion equivalents under LB catalysis.
LB-Enhanced nucleophilicity for M-M´ = Si-Si, Si-B, Sn-Sn, B-B
APPLICATIONS: ENHANCED ELECTROPHILICITY AND DUAL ACTIVATION BY LEWIS BASE (n-sigma )
LB catalyzed reactions of SiX3-based reagents with C=O, C=N
Aldolization
Reductions using HSiX3-based reagents
Reactions of epoxides
LEWIS BASE CATALYZED GENERATION OF ELECTROPHILIC INTERMEDIATES
Y-X + LB -¨electrophilic reagents for enantioselective addition to alkenes (n-sigma )
BIFUNCTIONAL (AND MULTIFUNCTIONAL) CATALYSIS
Bifunctional activation in reactions involving Lewis acid catalysis and Lewis base assisted bond polarization (n-sigma )
Bifunctional catalysis with Lewis base containing X-H sites that facilitate proton transfer or hydrogen bonding
CARBENES:LEWIS BASE CATALYSIS TRIGGERS MULTIPLE ACTIVATION PATHWAYS
Catalysis with Stable Carbenes
Summation