This two–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. INDICE: 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
- ISBN: 978-3-527-33618-0
- Editorial: Wiley VCH
- Encuadernacion: Cartoné
- Páginas: 1488
- Fecha Publicación: 13/07/2016
- Nº Volúmenes: 1
- Idioma: Inglés