Wiley-VCH - Books | Chemistry | Organic Chemistry | Aziridines and Epoxides in Organic Synthesis

	Books \| Chemistry \| Organic Chemistry \| Aziridines and Epoxides in Organic Synthesis \| Table of contents

Books

	Just published
	Title search
	Featured sites
	Entertainment

Journals

Electronic Media

	Table of Contents


	Foreword	VII
	Preface	XVII
	List of Contributors	XIX
1	Asymmetric Synthesis of Epoxides and Aziridines from Aldehydes and Imines Varinder K. Aggarwal, D. Michael Badine, and Vijayalakshmi A. Moorthie	1
1.1	Introduction	1
1.2	Asymmetric Epoxidation of Carbonyl Compounds	1
1.2.1	Aryl, Vinyl, and Alkyl Epoxides	2
1.2.1.1	Stoichiometric Ylide-mediated Epoxidation	2
1.2.1.2	Catalytic Ylide-mediated Epoxidation	3
1.2.1.3	Discussion of Factors Affecting Diastereo- and Enantioselectivity	8
1.2.2	Terminal Epoxides	10
1.2.3	Epoxy Esters, Amides, Acids, Ketones, and Sulfones	11
1.2.3.1	Sulfur Ylide-mediated Epoxidation	11
1.2.3.2	Darzens Reaction	13
1.2.3.3	Darzens Reactions in the Presence of Chiral Auxiliaries	13
1.2.3.4	Darzens Reactions with Chiral Reagents	18
1.2.3.5	Darzens Reactions with Chiral Catalysts	20
1.3	Asymmetric Aziridination of Imines	22
1.3.1	Aziridines Bearing Electron-withdrawing Groups: Esters and Amides	23
1.3.1.1	Aza-Darzens Route	23
1.3.1.2	Reactions between Imines and Carbenes	24
1.3.1.3	Aziridines by Guanidinium Ylide Chemistry	27
1.3.2	Aziridines Bearing Alkyl, Aryl, Propargyl, and Vinyl Groups	28
1.3.2.1	Aryl, Vinyl, and Alkyl Aziridines: Stoichiometric Asymmetric Ylide-mediated Aziridination	28
1.3.2.2	Aryl, Vinyl, and Alkyl Aziridines: Catalytic Asymmetric Ylide-mediated Aziridination	31
1.4	Summary and Outlook	33
	References	34
2	Vinylaziridines in Organic Synthesis Hiroaki Ohno	37
2.1	Introduction	37
2.2	Direct Synthesis of Vinylaziridines [1]	37
2.2.1	Addition of Nitrene to Dienes	37
2.2.2	Addition of Allylic Ylides and Related Reagents to Imines	39
2.2.3	Cyclization of Amino Alcohols and Related Compounds	42
2.2.4	Cyclization of Amino Allenes	45
2.2.5	Aziridination of ,-unsaturated Oximes and Hydrazones	46
2.3	Ring-opening Reactions with Nucleophiles	47
2.3.1	Hydride Reduction	47
2.3.2	Organocopper-mediated Alkylation	48
2.3.3	Reactions with Oxygen Nucleophiles	51
2.3.4	Reactions with Other Nucleophiles	54
2.4	Isomerization Including Rearrangement	54
2.4.1	Aza-[3,3]-Claisen Rearrangement	55
2.4.2	Pyrroline Formation	57
2.4.3	Aza-[2,3]-Wittig Rearrangement	60
2.4.4	Hydrogen Shift	61
2.4.5	Rearrangement with an Aryl Group on the Aziridine Carbon	62
2.4.6	Epimerization	63
2.5	Cycloaddition	64
2.5.1	Cycloadditions of Isocyanates and Related Compounds	64
2.5.2	Carbonylative Ring-expansion to Lactams	65
2.6	Electron Transfer to Vinylaziridines	67
2.7	Conclusions	68
	References	68
3	Asymmetric Syntheses with Aziridinecarboxylate and Aziridinephosphonate Building Blocks Ping Zhou, Bang-Chi Chen, and Franklin A. Davis	73
3.1	Introduction	73
3.2	Preparation of Aziridine-2-carboxylates and Aziridine-2-phosphonates	74
3.2.1	Preparation of Aziridine-2-carboxylates	74
3.2.1.1	Cyclization of Hydroxy Amino Esters	74
3.2.1.2	Cyclization of Hydroxy Azido Esters	76
3.2.1.3	Cyclization of -Halo- and -Sulfonyloxy--amino Esters and Amides	76
3.2.1.4	Aziridination of ,-unsaturated Esters	77
3.2.1.5	Aziridination of Imines	79
3.2.1.6	Aziridination of Aldehydes	82
3.2.1.7	2-Carboxylation of Aziridines	83
3.2.1.8	Resolution of Racemic Aziridine-2-carboxylates	84
3.2.2	Preparation of Aziridine-2-phosphonates	85
3.3	Reactions of Aziridine-2-carboxylates and Aziridine-2-phosphonates	87
3.3.1	Reactions of Aziridine-2-carboxylates	87
3.3.1.1	Reductive Ring-opening	88
3.3.1.2	Base-promoted Ring-opening	89
3.3.1.3	Nucleophilic Ring-opening	89
3.3.1.4	Electrophilic Substitutions at the C-2 Carbon Atom	97
3.3.1.5	Ring-expansion Reactions	98
3.3.1.6	Conversion to Azirine-2-carboxylates	102
3.3.2	Reactions of Aziridine-2-phosphonates	103
3.4	Applications in Natural Product Syntheses	105
3.5	Summary and Conclusions	111
	References	112
4	Synthesis of Aziridines Dedicated, with respect, to Professor Sir Charles Rees, FRS Joseph B. Sweeney	117
4.1	Introduction	117
4.2	Overview and General Features	117
4.2.1	Addition to Alkenes	118
4.2.1.1	Addition of Nitrenes and Nitrenoids to Alkenes	119
4.2.1.2	Aziridines by Addition-elimination Processes	128
4.2.2	Addition to Imines	129
4.2.2.1	Carbene Methodology	129
4.2.2.2	Aza-Darzens and Analogous Reactions	132
4.2.3	Addition to Azirines	134
4.2.4	Aziridines through Cyclization	139
4.2.4.1	From Epoxides	139
4.2.4.2	From 1,2-Aminoalcohols and 1,2-Aminohalides	140
4.2.4.3	From 1,2-Azidoalcohols [2, 3]	141
4.3	Conclusions	141
	References	142
5	Metalated Epoxides and Aziridines in Synthesis David M. Hodgson and Christopher D. Bray	145
5.1	Introduction	145
5.2	Metalated Epoxides	146
5.2.1	C–H Insertions	147
5.2.1.1	Transannular C–H Insertions in Epoxides of Medium-sized Cycloalkenes	147
5.2.1.2	Transannular C–H Insertions in Epoxides of Polycyclic Alkenes	151
5.2.1.3	Nontransannular Examples of C–H Insertion	152
5.2.1.4	Isomerization of Epoxides to Ketones	153
5.2.2	Cyclopropanations	155
5.2.3	Olefin Formation	157
5.2.4	Electrophile Trapping	163
5.2.4.1	Introduction	163
5.2.4.2	Silyl-stabilized Lithiated Epoxides	164
5.2.4.3	Sulfonyl-stabilized Lithiated Epoxides	165
5.2.4.4	Organyl-stabilized Lithiated Epoxides	167
5.2.4.5	Remotely Stabilized Lithiated Epoxides	170
5.2.4.6	Simple Metalated Epoxides	171
5.3	Metalated Aziridines	172
5.3.1	Electrophile Trapping	173
5.3.1.1	Stabilized Metalated Aziridines	173
5.3.1.2	Nonstabilized Metalated Aziridines	175
5.3.2	Olefin Formation	177
5.3.3	C–H Insertions	178
5.4	Outlook	180
	References	180
6	Metal-catalyzed Synthesis of Epoxides Hans Adolfsson and Daniela Balan	185
6.1	Introduction	185
6.2	Oxidants Available for Selective Transition Metal-catalyzed Epoxidation	186
6.3	Epoxidations of Olefins Catalyzed by Early Transition Metals	188
6.3.1	Titanium-catalyzed Epoxidations	188
6.3.2	Vanadium-catalyzed Epoxidations	192
6.4	Chromium-, Molybdenum-, and Tungsten-catalyzed Epoxidations	195
6.4.1	Homogeneous Systems Using Molybdenum and Tungsten Catalysts and Alkyl Hydroperoxides or Hydrogen Peroxide as the Terminal Oxidant	196
6.4.2	Heterogeneous Catalysts	199
6.5	Manganese-catalyzed Epoxidations	201
6.5.1	Hydrogen Peroxide as Terminal Oxidant	201
6.5.2	Manganese-catalyzed Asymmetric Epoxidations	204
6.6	Rhenium-catalyzed Epoxidations	208
6.6.1	MTO as Epoxidation Catalyst – Original Findings	211
6.6.2	The Influence of Heterocyclic Additives	211
6.6.3	The Role of the Additive	214
6.6.4	Other Oxidants	215
6.6.5	Solvents/Media	217
6.6.6	Asymmetric Epoxidations with MTO	218
6.7	Iron-catalyzed Epoxidations	219
6.8	Ruthenium-catalyzed Epoxidations	221
6.9	Concluding Remarks	224
	References	225
7	Catalytic Asymmetric Epoxide Ring-opening Chemistry Lars P. C. Nielsen and Eric N. Jacobsen	229
7.1	Introduction	229
7.2	Enantioselective Nucleophilic Addition to Meso-Epoxides	229
7.2.1	Nitrogen-centered Nucleophiles	229
7.2.2	Sulfur-centered Nucleophiles	236
7.2.3	Oxygen-centered Nucleophiles	238
7.2.4	Carbon-centered Nucleophiles	243
7.2.5	Halide and Hydride Nucleophiles	247
7.3	Kinetic Resolution of Racemic Epoxides	250
7.3.1	Nitrogen-centered Nucleophiles	250
7.3.2	Oxygen-centered Nucleophiles	255
7.3.3	Carbon-centered Nucleophiles	261
7.4	Enantioselective Rearrangements of Epoxides	263
7.5	Conclusion	266
	References	266
8	Epoxides in Complex Molecule Synthesis Paolo Crotti and Mauro Pineschi	271
8.1	Introduction	271
8.2	Synthesis of Complex Molecules by Intramolecular Ring-opening of Epoxides with Heteronucleophiles	271
8.2.1	Intramolecular C–O Bond-forming Reactions	271
8.2.1.1	Synthesis of Substituted THF Rings	272
8.2.1.2	Synthesis of Substituted THP Rings	275
8.2.1.3	Intramolecular 5-exo and 6-endo Cyclization of Polyepoxides	282
8.2.2	Intramolecular C–N Bond-forming Reactions	286
8.3	Synthesis of Complex Molecules by Ring-opening of Epoxides with C-Nucleophiles	288
8.3.1	Intramolecular C–C Bond-forming Reactions	288
8.3.2	Intermolecular C–C Bond-forming Reactions	290
8.3.2.1	Intermolecular C–C Bond-forming Reactions with Organometallic Reagents	290
8.3.2.2	Addition Reactions of Metal Enolates of Non-stabilized Esters, Amides, and Ketones to Epoxides	295
8.4	Epoxy Glycals	299
8.5	Synthesis of Complex Molecules by Rearrangement Reactions of Epoxides	302
	References	309
9	Vinylepoxides in Organic Synthesis Berit Olofsson and Peter Somfai	315
9.1	Synthesis of Vinylepoxides	315
9.1.1	Vinylepoxides from Unfunctionalized Dienes	316
9.1.1.1	Epoxidation with Dioxiranes	316
9.1.1.2	Epoxidation with Mn-Salen Catalysts	318
9.1.1.3	Conversion of Diols into Epoxides	319
9.1.2	Vinylepoxides from Functionalized Dienes	320
9.1.2.1	From Dienones or Unsaturated Amides	320
9.1.2.2	From Dienols	321
9.1.3	Vinylepoxides from Epoxy Alcohols	322
9.1.4	Vinylepoxides from Aldehydes	324
9.1.4.1	Chloroallylboration	324
9.1.4.2	Reaction with Sulfur Ylides	326
9.1.5	Vinylepoxides from Other Substrates	327
9.1.5.1	From Allenes	327
9.1.5.2	Kinetic Resolution of Racemic Epoxides	328
9.2	Transformations of Vinylepoxides	329
9.2.1	Intermolecular Opening with Oxygen and Nitrogen Nucleophiles	329
9.2.1.1	1,2-Additions	329
9.2.1.2	1,4-Additions	331
9.2.2	Intramolecular Opening with Oxygen and Nitrogen Nucleophiles	332
9.2.3	Opening with Carbon Nucleophiles	335
9.2.3.1	S_N2’ Additions	335
9.2.3.2	S_N2 Additions	337
9.2.3.3	Regiodivergent Additions	338
9.2.4	Rearrangement Reactions	338
9.2.5	Hydrogenolysis	341
9.3	Conclusions	343
	References	343
10	The Biosynthesis of Epoxides Sabine Grüschow and David H. Sherman	349
10.1	Introduction	349
10.2	Cytochrome P450 Monooxygenases	350
10.2.1	Mechanism of Cytochrome P450 Monooxygenases	350
10.2.2	Epothilones	355
10.2.3	Mycinamicin	362
10.2.4	Griseorhodin A	364
10.2.5	Hedamycin	367
10.3	Flavin-dependent Epoxidases	368
10.3.1	Squalene Epoxidase	368
10.3.2	Styrene Epoxidase	373
10.4	Dioxygenases	376
10.5	Epoxidation through Dehydrogenation	383
10.5.1	Fosfomycin	383
10.5.2	Scopolamine	387
10.6	Dehalogenases	389
10.7	Summary and Outlook	394
	References	394
11	Aziridine Natural Products – Discovery, Biological Activity and Biosynthesis Philip A. S. Lowden	399
11.1	Introduction and Overview	399
11.2	Mitomycins and Related Natural Products	400
11.2.1	Discovery and Anticancer Properties	400
11.2.2	Mode of Action	401
11.2.3	Biosynthesis	406
11.3	The Azinomycins	414
11.3.1	Discovery and Anticancer Properties	414
11.3.2	Mode of Action	415
11.3.3	Biosynthesis	423
11.4	Other Aziridine Natural Products	428
11.4.1	Ficellomycin	428
11.4.2	593A/NSC-135758	428
11.4.3	Dicarboxyaziridine and Miraziridine A	429
11.4.4	Azicemicins	430
11.4.5	Maduropeptin	430
11.4.6	The Madurastatins	433
11.4.7	Aziridine Metabolites from Amino Alcohols	434
11.4.8	Azirine and Diazirine Natural Products	435
	References	437
12	Epoxides and Aziridines in Click Chemistry Valery V. Fokin and Peng Wu	443
12.1	Introduction	443
12.2	Epoxides in Click Chemistry	447
12.2.1	Synthesis of Epoxides	447
12.2.2	Nucleophilic Opening of Epoxides	451
12.3	Aziridines in Click Chemistry	455
12.3.1	Synthesis of Aziridines	455
12.3.1.1	Bromine-catalyzed Aziridination of Olefins with Chloramines	455
12.3.2.2	Aminohydroxylation followed by Cyclodehydration	459
12.3.2	Nucleophilic Opening of Aziridines	467
12.4	Aziridinium Ions in Click Chemistry	470
12.4.1	Generation of Aziridinium Ions	470
12.4.2	Nucleophilic Opening of Aziridinium Ions	471
12.4.2.1	Synthesis of Diamino Esters and -Lactams	472
12.4.2.2	Synthesis of Pyrazolo[1,2-]pyrazoles	473
	References	475
	Index	479

	Order
	Online book
	Table of contents
	Short description
	Detailed description
	Reviews
	Author information
	Author affiliation


	Aromaticity and Other Conjugation Effects Aromaticity and Other Conjugation Effects Handbook of Green Chemistry - Green Processes
	[more >>]


	Angewandte Chemie Angewandte Chemie International Edition Chemie Ingenieur Technik
[more>>]


	Christie, Daniel J. (ed.) The Encyclopedia of Peace Psychology 385.- Euro valid until 31 March 2012
	[more offers >>]

Tell a friend RSS Feeds Print-Version

©2012 Wiley-VCH Verlag GmbH & Co. KGaA - Provider
http://www.wiley-vch.de - mailto: info@wiley-vch.de
Data Protection