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9783527312139

Aziridines and Epoxides in Organic Synthesis

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  • ISBN13:

    9783527312139

  • ISBN10:

    3527312137

  • Edition: 1st
  • Format: Hardcover
  • Copyright: 2006-02-20
  • Publisher: Wiley-VCH

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Summary

Aziridines and epoxides are among the most widely used intermediates in organic synthesis, acting as precursors to complex molecules due to the strains incorporated in their skeletons. Besides their importance as reactive intermediates, many biologically active compounds also contain these three-membered rings.Filling a gap in the literature, this clearly structured book presents the much needed information in a compact and concise way. The renowned editor has succeeded in gathering together excellent authors to cover synthesis, applications, and the biological aspects in equal depth.Divided roughly equally between aziridines and epoxides, the twelve chapters discuss: Synthesis of aziridines Nucleophilic ring-opening of aziridines and epoxides Organic synthesis with aziridine building blocks Vinyl aziridines in organic synthesis Diastereoselective aziridination reagents Synthetic aspects of aziridinomitocene chemistry Biosynthesis of biologically important aziridines Organic catalysis of epoxide and aziridine ring formation Metal-mediated synthesis of epoxides Asymmetric epoxide ring opening chemistry Epoxides in complex molecule synthesis Biological activity of epoxide-containing moleculesA high-quality reference manual for academic and industrial chemists alike.

Author Biography

Professor Andrei K. Yudin obtained his PhD degree at the University of Southern California under the direction of Professors G. K. Surya Prakash and George A. Olah. He then took up a post-doctoral position in the laboratory of Professor K. Barry Sharpless at the Scripps Research Institute. In 1998, he started his independent career at the University of Toronto. His research interests are in transition metal catalysis, development of novel synthetic methods, and synthesis of complex heterocycles of biological significance.

Table of Contents

Foreword vii
Preface xvii
List of Contributors
xix
Asymmetric Synthesis of Epoxides and Aziridines from Aldehydes and Imines
1(36)
Varinder K. Aggarwal
D. Michael Badine
Vijayalakshmi A. Moorthie
Introduction
1(1)
Asymmetric Epoxidation of Carbonyl Compounds
1(21)
Aryl, Vinyl, and Alkyl Epoxides
2(1)
Stoichiometric Ylide-mediated Epoxidation
2(1)
Catalytic Ylide-mediated Epoxidation
3(5)
Discussion of Factors Affecting Diastereo- and Enantioselectivity
8(2)
Terminal Epoxides
10(1)
Epoxy Esters, Amides, Acids, Ketones, and Sulfones
11(1)
Sulfur Ylide-mediated Epoxidation
11(2)
Darzens Reaction
13(1)
Darzens Reactions in the Presence of Chiral Auxiliaries
13(5)
Darzens Reactions with Chiral Reagents
18(2)
Darzens Reactions with Chiral Catalysts
20(2)
Asymmetric Aziridination of Imines
22(11)
Aziridines Bearing Electron-withdrawing Groups: Esters and Amides
23(1)
Aza-Darzens Route
23(1)
Reactions between Imines and Carbenes
24(3)
Aziridines by Guanidinium Ylide Chemistry
27(1)
Aziridines Bearing Alkyl, Aryl, Propargyl, and Vinyl Groups
28(1)
Aryl, Vinyl, and Alkyl Aziridines: Stoichiometric Asymmetric Ylide-mediated Aziridination
28(3)
Aryl, Vinyl, and Alkyl Aziridines: Catalytic Asymmetric Ylide-mediated Aziridination
31(2)
Summary and Outlook
33(4)
References
34(3)
Vinylaziridines in Organic Synthesis
37(36)
Hiroaki Ohno
Introduction
37(1)
Direct Synthesis of Vinylaziridines [1]
37(10)
Addition of Nitrene to Dienes
37(2)
Addition of Allylic Ylides and Related Reagents to Imines
39(3)
Cyclization of Amino Alcohols and Related Compounds
42(3)
Cyclization of Amino Allenes
45(1)
Aziridination of α, β-unsaturated Oximes and Hydrazones
46(1)
Ring-opening Reactions with Nucleophiles
47(7)
Hydride Reduction
47(1)
Organocopper-mediated Alkylation
48(3)
Reactions with Oxygen Nucleophiles
51(3)
Reactions with Other Nucleophiles
54(1)
Isomerization Including Rearrangement
54(10)
Aza-[3,3]-Claisen Rearrangement
55(2)
Pyrroline Formation
57(3)
Aza-[2,3]-Wittig Rearrangement
60(2)
Hydrogen Shift
62(1)
Rearrangement with an Aryl Group on the Aziridine Carbon
62(1)
Epimerization
63(1)
Cycloaddition
64(3)
Cycloadditions of Isocyanates and Related Compounds
64(1)
Carbonylative Ring-expansion to Lactams
65(2)
Electron Transfer to Vinylaziridines
67(1)
Conclusions
68(5)
References
68(5)
Asymmetric Syntheses with Aziridinecarboxylate and Aziridine-phosphonate Building Blocks
73(44)
Ping Zhou
Bang-Chi Chen
Franklin A. Davis
Introduction
73(1)
Preparation of Aziridine-2-carboxylates and Aziridine-2-phosphonates
74(13)
Preparation of Aziridine-2-carboxylates
74(1)
Cyclization of Hydroxy Amino Esters
74(2)
Cyclization of Hydroxy Azido Esters
76(1)
Cyclization of α-Halo-and α-Sulfonyloxy-β-amino Esters and Amides
76(1)
Aziridination of α, β-unsaturated Esters
77(2)
Aziridination of Imines
79(3)
Aziridination of Aldehydes
82(1)
2-Carboxylation of Aziridines
83(1)
Resolution of Racemic Aziridine-2-carboxylates
84(1)
Preparation of Aziridine-2-phosphonates
85(2)
Reactions of Aziridine-2-carboxylates and Aziridine-2-phosphonates
87(18)
Reactions of Aziridine-2-carboxylates
87(1)
Reductive Ring-opening
88(1)
Base-promoted Ring-opening
89(1)
Nucleophilic Ring-opening
89(8)
Electrophilic Substitutions at the C-2 Carbon Atom
97(1)
Ring-expansion Reactions
98(4)
Conversion to Azirine-2-carboxylates
102(1)
Reactions of Aziridine-2-phosphonates
103(2)
Applications in Natural Product Syntheses
105(6)
Summary and Conclusions
111(6)
References
112(5)
Synthesis of Aziridines
117(28)
Sir Charles Rees
Joseph B. Sweeney
Introduction
117(1)
Overview and General Features
117(24)
Addition to Alkenes
118(1)
Addition of Nitrenes and Nitrenoids to Alkenes
119(9)
Aziridines by Addition-elimination Processes
128(1)
Addition to Imines
129(1)
Carbene Methodology
129(3)
Aza-Darzens and Analogous Reactions
132(2)
Addition to Azirines
134(5)
Aziridines through Cyclization
139(1)
From Epoxides
139(1)
From 1,2-Aminoalcohols and 1,2-Aminohalides
140(1)
From 1,2-Azidoalcohols [2, 3]
141(1)
Conclusions
141(4)
References
142(3)
Metalated Epoxides and Aziridines in Synthesis
145(40)
David M. Hodgson
Christopher D. Bray
Introduction
145(1)
Metalated Epoxides
146(26)
C--H Insertions
147(1)
Transannular C--H Insertions in Epoxides of Medium-sized Cycloalkenes
147(4)
Transannular C--H Insertions in Epoxides of Polycyclic Alkenes
151(1)
Nontransannular Examples of C--H Insertion
152(1)
Isomerization of Epoxides to Ketones
153(2)
Cyclopropanations
155(2)
Olefin Formation
157(6)
Electrophile Trapping
163(1)
Introduction
163(1)
Silyl-stabilized Lithiated Epoxides
164(1)
Sulfonyl-stabilized Lithiated Epoxides
165(2)
Organyl-stabilized Lithiated Epoxides
167(3)
Remotely Stabilized Lithiated Epoxides
170(1)
Simple Metalated Epoxides
171(1)
Metalated Aziridines
172(8)
Electrophile Trapping
173(1)
Stabilized Metalated Aziridines
173(2)
Nonstabilized Metalated Aziridines
175(2)
Olefin Formation
177(1)
C--H Insertions
178(2)
Outlook
180(5)
References
180(5)
Metal-catalyzed Synthesis of Epoxides
185(44)
Hans Adolfsson
Daniela Balan
Introduction
185(1)
Oxidants Available for Selective Transition Metal-catalyzed Epoxidation
186(2)
Epoxidations of Olefins Catalyzed by Early Transition Metals
188(7)
Titanium-catalyzed Epoxidations
188(4)
Vanadium-catalyzed Epoxidations
192(3)
Chromium-, Molybdenum-, and Tungsten-catalyzed Epoxidations
195(6)
Homogeneous Systems Using Molybdenum and Tungsten Catalysts and Alkyl Hydroperoxides or Hydrogen Peroxide as the Terminal Oxidant
196(3)
Heterogeneous Catalysts
199(2)
Manganese-catalyzed Epoxidations
201(7)
Hydrogen Peroxide as Terminal Oxidant
201(3)
Manganese-catalyzed Asymmetric Epoxidations
204(4)
Rhenium-catalyzed Epoxidations
208(11)
MTO as Epoxidation Catalyst--Original Findings
211(1)
The Influence of Heterocyclic Additives
211(3)
The Role of the Additive
214(1)
Other Oxidants
215(2)
Solvents/Media
217(1)
Asymmetric Epoxidations with MTO
218(1)
Iron-catalyzed Epoxidations
219(2)
Ruthenium-catalyzed Epoxidations
221(3)
Concluding Remarks
224(5)
References
225(4)
Catalytic Asymmetric Epoxide Ring-opening Chemistry
229(42)
Lars P. C. Nielsen
Eric N. Jacobsen
Introduction
229(1)
Enantioselective Nucleophilic Addition to Meso-Epoxides
229(21)
Nitrogen-centered Nucleophiles
229(7)
Sulfur-centered Nucleophiles
236(2)
Oxygen-centered Nucleophiles
238(5)
Carbon-centered Nucleophiles
243(4)
Halide and Hydride Nucleophiles
247(3)
Kinetic Resolution of Racemic Epoxides
250(13)
Nitrogen-centered Nucleophiles
250(5)
Oxygen-centered Nucleophiles
255(6)
Carbon-centered Nucleophiles
261(2)
Enantioselective Rearrangements of Epoxides
263(3)
Conclusion
266(5)
References
266(5)
Epoxides in Complex Molecule Synthesis
271(44)
Paolo Crotti
Mauro Pineschi
Introduction
271(1)
Synthesis of Complex Molecules by Intramolecular Ring-opening of Epoxides with Heteronucleophiles
271(17)
Intramolecular C--O Bond-forming Reactions
271(1)
Synthesis of Substituted THF Rings
272(3)
Synthesis of Substituted THP Rings
275(7)
Intramolecular 5-exo and 6-endo Cyclization of Polyepoxides
282(4)
Intramolecular C--N Bond-forming Reactions
286(2)
Synthesis of Complex Molecules by Ring-opening of Epoxides with C-Nucleophiles
288(11)
Intramolecular C--C Bond-forming Reactions
288(2)
Intermolecular C--C Bond-forming Reactions
290(1)
Intermolecular C--C Bond-forming Reactions with Organometallic Reagents
290(5)
Addition Reactions of Metal Enolates of Non-stabilized Esters, Amides, and Ketones to Epoxides
295(4)
Epoxy Glycals
299(3)
Synthesis of Complex Molecules by Rearrangement Reactions of Epoxides
302(13)
References
309(6)
Vinylepoxides in Organic Synthesis
315(34)
Berit Olofsson
Peter Somfai
Synthesis of Vinylepoxides
315(14)
Vinylepoxides from Unfunctionalized Dienes
316(1)
Epoxidation with Dioxiranes
316(2)
Epoxidation with Mn-Salen Catalysts
318(1)
Conversion of Diols into Epoxides
319(1)
Vinylepoxides from Functionalized Dienes
320(1)
From Dienones or Unsaturated Amides
320(1)
From Dienols
321(1)
Vinylepoxides from Epoxy Alcohols
322(2)
Vinylepoxides from Aldehydes
324(1)
Chloroallylboration
324(2)
Reaction with Sulfur Ylides
326(1)
Vinylepoxides from Other Substrates
327(1)
From Allenes
327(1)
Kinetic Resolution of Racemic Epoxides
328(1)
Transformations of Vinylepoxides
329(14)
Intermolecular Opening with Oxygen and Nitrogen Nucleophiles
329(1)
1,2-Additions
329(2)
1,4--Additions
331(1)
Intramolecular Opening with Oxygen and Nitrogen Nucleophiles
332(3)
Opening with Carbon Nucleophiles
335(1)
SN2' Additions
335(2)
SN2 Additions
337(1)
Regiodivergent Additions
338(1)
Rearrangement Reactions
338(3)
Hydrogenolysis
341(2)
Conclusions
343(6)
References
343(6)
The Biosynthesis of Epoxides
349(50)
Sabine Gruschow
David H. Sherman
Introduction
349(1)
Cytochrome P450 Monooxygenases
350(18)
Mechanism of Cytochrome P450 Monooxygenases
350(5)
Epothilones
355(7)
Mycinamicin
362(2)
Griseorhodin A
364(3)
Hedamycin
367(1)
Flavin-dependent Epoxidases
368(8)
Squalene Epoxidase
368(5)
Styrene Epoxidase
373(3)
Dioxygenases
376(7)
Epoxidation through Dehydrogenation
383(6)
Fosfomycin
383(4)
Scopolamine
387(2)
Dehalogenases
389(5)
Summary and Outlook
394(5)
References
394(5)
Aziridine Natural Products--Discovery, Biological Activity and Biosynthesis
399(44)
Philip A. S. Lowden
Introduction and Overview
399(1)
Mitomycins and Related Natural Products
400(14)
Discovery and Anticancer Properties
400(1)
Mode of Action
401(5)
Biosynthesis
406(8)
The Azinomycins
414(14)
Discovery and Anticancer Properties
414(1)
Mode of Action
415(8)
Biosynthesis
423(5)
Other Aziridine Natural Products
428(15)
Ficellomycin
428(1)
593A/NSC-135758
428(1)
Dicarboxyaziridine and Miraziridine A
429(1)
Azicemicins
430(1)
Maduropeptin
430(3)
The Madurastatins
433(1)
Aziridine Metabolites from Amino Alcohols
434(1)
Azirine and Diazirine Natural Products
435(2)
References
437(6)
Epoxides and Aziridines in Click Chemistry
443(36)
Valery V. Fokin
Peng Wu
Introduction
443(4)
Epoxides in Click Chemistry
447(8)
Synthesis of Epoxides
447(4)
Nucleophilic Opening of Epoxides
451(4)
Aziridines in Click Chemistry
455(15)
Synthesis of Aziridines
455(1)
Bromine-catalyzed Aziridination of Olefins with Chloramines
455(4)
Aminohydroxylation followed by Cyclodehydration
459(8)
Nucleophilic Opening of Aziridines
467(3)
Aziridinium Ions in Click Chemistry
470(9)
Generation of Aziridinium Ions
470(1)
Nucleophilic Opening of Aziridinium Ions
471(1)
Synthesis of Diamino Esters and β-Lactams
472(1)
Synthesis of Pyrazolo[1,2-α]pyrazoles
473(2)
References
475(4)
Index 479

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