Modern Catalytic Methods for Organic Synthesis with Diazo Compounds From Cyclopropanes to Ylides,9780471135562

Modern Catalytic Methods for Organic Synthesis with Diazo Compounds From Cyclopropanes to Ylides

by ; ;
Edition: 1st
ISBN13: 9780471135562
ISBN10: 0471135569
Format: Hardcover
Pub. Date: 1998-01-19
Publisher(s): Wiley-Interscience
  • Free Shipping Icon

    This Item Qualifies for Free Shipping!*

    *Excludes marketplace orders.

List Price: $402.01

Buy New

Arriving Soon. Will ship when available.
$382.87
Add to Cart

Rent Textbook

Select for Price
Add to Cart
There was a problem. Please try again later.

Used Textbook

We're Sorry
Sold Out

eTextbook

We're Sorry
Not Available

Buy from our Marketplace starting at $135.74

How Marketplace Works:

  • This item is offered by an independent seller and not shipped from our warehouse
  • Item details like edition and cover design may differ from our description; see seller's comments before ordering.
  • Sellers much confirm and ship within two business days; otherwise, the order will be cancelled and refunded.
  • Marketplace purchases cannot be returned to eCampus.com. Contact the seller directly for inquiries; if no response within two days, contact customer service.
  • Additional shipping costs apply to Marketplace purchases. Review shipping costs at checkout.

Summary

This much-needed resource brings together a wealth of procedures for the synthesis and practical use of diazocarbonyl compounds. It features methods for the preparation of important catalysts and for applications of diazocarbonyl compounds within each of the main transformation categories-including in-depth coverage of cyclopropanation, C-H and X-H insertion, Wolff rearrangement, ylide formation, aromatic cycloaddition and substitution, and many other useful reactions. Written by leading experts in the field, this book contains cutting-edge material on highly enantioselective transformations, and presents new ways of thinking about diazocarbonyl compounds and their applications, from donor-acceptor cyclopropanes in organic synthesis to macrocyclic cyclopropanation. Complete with illustrative examples of procedures in each chapter, clear diagrams, and a detailed bibliography, this practical reference gives readers the tools they need to put diazocarbonyl compounds to work for their own projects-an invaluable source of guidance for synthetic organic chemists, chemical scientists, and advanced students.

Author Biography

MICHAEL P. DOYLE, PhD, was D. R. Semmes Professor of Chemistry at Trinity University in San Antonio, Texas, and is currently Professor of Chemistry at the University of Arizona in Tucson. M.<br> <br> Y McKERVEY, PhD, is Professor of Chemistry and Director of QUCHEM at Queen's University in Belfast, Northern Ireland. TAO YE, PhD, is a Postdoctoral Fellow in the Department of Chemistry at the University of Nottingham in Great Britain.

Table of Contents

Preface xv(2)
Acknowledgements xvii
1. Synthesis of XXX-Diazocarbonyl Compounds
1(60)
1.1 Introduction
1(1)
1.2 Acylation of Diazoalkanes
1(8)
Preparation of Diazomethane from Diazald
4(2)
Preparation of a Diazoketone from an Acid Chloride: Synthesis of I-Diazo-4-phenyl-2-butanone
6(1)
Preparation of a Diazoketone from Mixed Carbonic Anhydrides: Synthesis of N-tert-Butoxycarbonyl-L-Phenylalanyl Diazomethane
7(2)
1.3 Diazo Transfer Reactions
9(23)
1.3.1 Simple Diazo Transfer Reactions
9(2)
Simple Diazo Transfer Reaction: Synthesis of tert-Butyl XXX-Diazoacetoacetate
10(1)
1.3.2 Deformylating Diazo Transfer and Related Modifications
11(10)
Deformylating Diazo Transfer Reaction: Synthesis of 2-Diazocyclohexanone
12(4)
Detrifluoroacetylating Diazo Transfer: Synthesis of (E)-1-Diazo-4-Phenyl-3-Buten-2-one
16(5)
1.3.3 Effects of Base and Solvent on Diazo Transfer
21(4)
Direct Diazo Transfer Using 2,4,6-Triisopropylphenylsulfonyl Azide: Synthesis of 2-Diazo-5-methoxy-1-tetralone
24(1)
1.3.4 Effects of Transfer Reagent on Diazo Transfer and Hazards Evaluation
25(7)
Synthesis of 4-Dodecylbenzenesulfonyl Azide
26(6)
1.4 Other Routes to Diazocarbonyl Compounds
32(8)
Glyoxylic Acid Chloride p-Toluenesulfonylhydrazone: Preparation of Diazoester 158
37(3)
1.5 Chemical Modification of Diazocarbonyl Compounds
40(5)
1.6 Conclusion: Safety and Handling of Diazocarbonyl Compounds
45(1)
1.7 References
46(15)
2. Catalysts for Metal Carbene Transformations
61(51)
2.1 Electrophilic Addition to Diazo Compounds
61(1)
2.2 Mechanism of Catalytic Diazo Decomposition. Metal Carbene Generation and Reactions
62(4)
2.3 Mechanism of Catalytic Diazo Decomposition. Electrophilic Addition by Metal Olefin Complexes
66(2)
2.4 Copper Catalysts for Diazo Decomposition
68(5)
2.4.1 Oxidation States for Copper
68(1)
2.4.2 Ligands for Copper
69(4)
Ligand Preparation
72(1)
2.5 Cobalt Catalysts for Diazo Decomposition
73(1)
2.6 Palladium Catalysts for Diazo Decomposition
74(1)
2.7 Rhodium Catalysts for Diazo Decomposition
75(17)
2.7.1 Dirhodium(II) Carboxylates
75(6)
Rhodium(II) Perfluorobutyrate
77(2)
Dirhodium(II) Tetrakis[4-tert-butyl-N-benzenesulfonyl-L-prolinate]
79(2)
2.7.2 Dirhodium(II) Carboxamidates
81(9)
Dirhodium(II) Caprolactamate
83(5)
Dirhodium(II) Tetrakis[methyl 2-oxooxazolidine-4(S)-carboxylate], Rh(2)(4S-MEOX)(4)
88(2)
2.7.3 Hexarhodium Hexadecacarbonyl
90(1)
2.7.4 Dirhodium(II) Phosphates and Orthometallated Phosphines
90(1)
2.7.5 Rhodium(III) Porphyrins
91(1)
2.8 Ruthenium Catalysts for Diazo Decomposition
92(2)
2.9 Other Transition Metals as Catalysts for Diazo Decomposition
94(3)
2.9.1 Osmium
94(1)
2.9.2 Iron
94(1)
2.9.3 Plantinum and Nickel
95(1)
2.9.4 The Chromium Triad
96(1)
2.10 Metal Carbenes as Stoichiometric Reagents
97(2)
2.11 References
99(13)
3. Insertion Reactions
112(51)
3.1 Catalytic Intermolecular Carbon-Hydrogen Insertion Reactions
114(1)
3.2 Catalytic Intramolecular Carbon-Hydrogen Insertion Reactions: General Considerations
115(2)
3.3 Catalytic Intramolecular Carbon-Hydrogen Insertion Reactions of Diazoketones: Regioselectivity for Cyclopentanone Formation
117(4)
3.4 Catalytic Intramolecular Carbon-Hydrogen Insertion Reactions of Diazoketones and Diazoesters: Diastereoselectivity and Synthetic Applications
121(4)
3.5 Catalytic Intramolecular Carbon-Hydrogen Insertion Reactions of Diazoacetates: Lactone Formation Catalytic Dinitrogen Extrusion from l-(-)-Menthyle Diazoacetoacetate
128(1)
3.6 Catalytic Intramolecular Carbon-Hydrogen Insertion Reactions of Diazoacetamides: Lactam Formation
129(3)
3.7 Catalyst-Dependent Chemoselectivity and Regioselectivity for Carbon-Hydrogen Insertion
132(4)
3.8 Enantioselectivity in Intramolecular Carbon-Hydrogen Insertion Reactions
136(11)
Synthesis of (+)-Arctigenin
140(5)
Synthesis of (4R, 5R)-(+)-2-Deoxyxylolactone
145(2)
3.9 Diastereoselection and Regioselection in Carbon-Hydrogen Insertion Reactions Promoted by Chiral Catalysts
147(3)
3.10 Diastereoselection in Carbon-Hydrogen Insertion Reactions Controlled with the Use of Chiral Auxiliaries
150(1)
3.11 Silicon-Hydrogen and Related Insertion Reactions
151(2)
3.12 References
153(10)
4. Intermolecular Cyclopropanation and Related Addition Reactions
163(75)
4.1 Cyclopropanation with Diazomethane
163(4)
4.2 Cyclopropanation Reactions with Diazocarbonyl Compounds. General
167(2)
4.3 Intermolecular Cyclopropanation Reactions of Diazocarbonyl Compounds. Diastereoselectivity
169(7)
2,6-Di-tert-butyl-4-methylphenyl Diazoacetate (BDA)
173(3)
4.4 Intermolecular Cyclopropanation Reactions of Diazocarbonyl Compounds. Regioselectivity and Relative Reactivities
176(2)
4.5 Mechanism of Cyclopropanation. Stereochemistry of Cyclopropane Formation
178(5)
4.6 Intermolecular Cyclopropanation Reactions of Diazocarbonyl Compounds. Enantioselectivity
183(16)
4.6.1 Salicylaldimine-Copper Catalysts
183(2)
4.6.2 Semicorrin-Copper Catalysts
185(2)
4.6.3 bis(Oxazoline)-Copper Catalysts
187(2)
4.6.4 Pyridine-Ligated Copper Catalysts
189(1)
4.6.5 Other Chiral Copper Catalysts
190(1)
4.6.6 Chiral Dirhodium(II) Carboxylates
191(2)
4.6.7 Chiral Dirhodium(II) Carboxamidates
193(3)
4.6.8 Other Chiral Rhodium Catalysts
196(1)
4.6.9 Pybox-Ruthenium Catalysts
197(1)
4.6.10 Cobalt Catalysts
198(1)
4.7 Donor-Acceptor Cyclopropanes in Organic Synthesis
199(4)
4.8 Vinyldiazoacetates--Intermolecular Annulation Reactions
203(3)
4.8.1 Formal [3+4]-Cycloaddition
203(2)
4.8.2 Formal [3+2]-Cycloaddition
205(1)
4.9 1,3-Dipolar Ketocarbene Addition
206(3)
4.10 Intermolecular Cyclopropanation and Subsequent Reactions in Synthesis
209(3)
4.11 Cyclopropenation of Alkynes
212(4)
4.12 Aziridination
216(4)
4.12.1 Addition to Imines
217(1)
4.12.2 Nitrene Addition to Alkenes
218(2)
4.13 References
220(18)
5. Intramolecular Cyclopropanation and Related Addition Reactions
238(51)
5.1 Intramolecular Cyclopropanation of Diazoketones
239(6)
5.2 Vinylcyclopropylcarbonyl Compounds in Organic Synthesis
245(1)
5.3 Intramolecular Cyclopropanation of Diazoesters and Diazoamides
246(6)
5.4 Regioselectivity and Chemoselectivity in Intramolecular Cyclopropanation Reactions
252(3)
5.5 Enantioselective Intramolecular Cyclopropanation Reactions
255(14)
Synthesis of (1R, 5S)-(-)-6,6-Dimethyl-3-oxabicyclo-[3.1.0]hexan-2-one
259(4)
Synthesis of (1S, 5R)-(+)-3,6,6-Trimethyl-3-azabicyclo-[3.1.0]hexan-2-one
263(6)
5.6 Diastereocontrol in Intramolecular Cyclopropanation Reactions
269(2)
5.7 Macrocyclic Cyclopropanation
271(4)
5.8 Intramolecular Cyclopropenation Reactions: Tandem/Cascade Processes
275(4)
5.9 References
279(10)
6. Cycloaddition and Substitution Reactions with Aromatic and Heteroaromatic Compounds
289(66)
6.1 Intermolecular Reactions with Benzene and its Derivatives
289(9)
6.1.1 Diazoesters
289(5)
6.1.2 Diazoketones
294(4)
6.2 Intramolecular Cycloaddition Reactions with Benzene Derivatives
298(27)
6.2.1 Diazoketones
298(19)
Diazoketone Cyclization onto a Benzene Ring: 3,4-Dihydro-1(2H)-Azulenone [1(2H)-Azulenone, 3,4-dihydro-]
300(17)
6.2.2 Diazoesters and Diazoamides
317(3)
6.2.3 Chemoselectivity in Aromatic Cycloaddition
320(4)
6.2.4 Asymmetric Synthesis in Aromatic Cycloaddition
324(1)
6.3 Substitution Reactions with Aromatic Compounds
325(11)
Rhodium(II) Acetate-Catalyzed Decomposition of 2-Diazo-3-oxobutanamides
327(3)
6.3.1 Chemoselectivity in Aromatic Substitution
330(4)
6.3.2 Asymmetric Synthesis in Aromatic Substitution
334(2)
6.4 Cycloaddition and Substitution Reactions with Heterocyclic Aromatic Compounds
336(12)
6.4.1 Furans
336(9)
Reaction of EDA with Furan
339(6)
6.4.2 Pyrroles
345(2)
6.4.3 Thiophenes
347(1)
6.5 References
348(7)
7. Generation and Reactions of Ylides from Diazocarbonyl Compounds
355(78)
7.1 Introduction
355(1)
7.2 Formation of Sulfur Ylides
356(21)
7.2.1 Formation of Stable Sulfonium and Sulfoxonium Ylides from Diazocarbonyl Precursors
357(2)
7.2.2 Intramolecular Formation of Sulfur Ylides and Subsequent Reactions
359(8)
Reaction of 2-Phenyl-1,3-dithiane with EDA
364(3)
7.2.3 Intramolecular Formation of Sulfur Ylides and Subsequent Reactions
367(5)
7.2.4 XXX-Elimination and Related [1,4] Rearrangement
372(3)
7.2.5 Chemo-and Stereoselectivity in Sulfur Ylide Formation and Subsequent Rearrangement
375(2)
7.3 Formation of Oxonium Ylides
377(13)
7.3.1 Intermolecular Formation of Oxonium Ylides and Subsequent Reactions
379(1)
7.3.2 Intramolecular Formation of Oxonium Ylides and Subsequent Reactions
380(6)
[2,3]-Sigmatropic Rearrangement of Cyclic Oxonium Ylide: Synthesis of 8-Chloro-5,7-dimethoxy-2-carbomethoxy-2-[1-(S)-methyl-2-butenyl]benzofuran-3-one
383(3)
7.3.3 Chemo-, Diastereo-, and Enantioselectivity in Oxonium Ylide Formation
386(4)
7.4 Formation of Nitrogen Ylides from Diazocarbonyl Compounds
390(7)
7.4.1 Intermolecular Formation of Nitrogen Ylides and Subsequent Reactions
390(2)
7.4.2 Intramolecular Formation of Nitrogen Ylides and Subsequent Reactions
392(5)
7.5 Formation of Carbonyl Ylides from Diazocarbonyl Compounds
397(19)
7.5.1 Intermolecular Carbonyl Ylide Formation and Subsequent Reactions
398(1)
7.5.2 Intramolecular Carbonyl Ylide Formation and Subsequent Reactions
399(13)
Intramolecular Carbonyl Ylide Formation and Subsequent 1,3-Dipolar Cycloaddition Reaction: Synthesis of 6,8-Dioxabicyclo[3.2.1]octane Ring Systems
403(9)
7.5.3 Chemoselectivity in Carbonyl Ylide Formation
412(4)
7.6 Formation of Thiocarbonyl Ylides from Diazocarbonyl Compounds
416(5)
7.7 References
421(12)
8. X-H Insertion Reactions of Diazocarbonyl Compounds (X = N, O, S, Se, P, Halogen)
433(54)
8.1 Introduction
433(3)
8.2 N-H Insertion
436(9)
8.2.1 Intermolecular N-H Reactions
436(2)
8.2.2 Intramolecular N-H Insertion
438(6)
8.2.3 Asymmetric N-H Insertion
444(1)
8.3 O-H Insertion with Water, Alcohols, and Phenols
445(19)
8.3.1 Intermolecular O-H Insertion
445(13)
2-Isopropoxycyclohexanone
451(7)
8.3.2 Intramolecular O-H Insertion
458(4)
8.3.3 Asymmetric O-H Insertion
462(2)
8.4 O-H Insertion Reactions with Carboxylic Acids, Carboxylic Esters, and Sulfonic Acids
464(4)
(S)-3-N-(Phthalimido)-4-phenyl-1-(methane-sulfonyloxy)butan-2-one
467(1)
8.5 S-H Insertion
468(5)
2-(Phenylthio)-6-phenyl-3-hexanone
472(1)
8.6 Se-H Insertion
473(1)
8.7 P-H Insertion
474(1)
8.8 X-H Insertion (X = Halogen)
474(2)
8.9 References
476(11)
9. The Wolff Rearrangement and Related Reactions
487(47)
9.1 The Arndt-Eistert Homologation
488(15)
Ethyl 1-Naphthylacetate
489(2)
3(S)-Methyl-3-(N-tert-butoxycarbonylamino)-6-(N-bis-benzyloxycarbonyl guanidyl)hexanoate
491(5)
Protected Homopeptide
496(7)
9.2 Ring Contraction via the Wolff Rearrangement
503(11)
Formation and Photochemical Wolff Rearrangement of Cyclic XXX-Diazoketones: D-Norandrost-5-en-3XXX-ol-16-carboxylic Acids
512(2)
9.3 The Wolff Rearrangement with Cycloaddition Reactions
514(6)
9.4 The Vinylogous Wolff Rearrangement
520(1)
9.5 Miscellaneous Applications of the Wolff Rearrangement
521(3)
9.6 Conclusions
524(1)
9.7 References
525(9)
10. Reactions of XXX-Diazocarbonyl Compounds with Aldehydes and Ketones
534(34)
10.1 Introduction
534(1)
10.2 Base Promoted Reactions of XXX-Diazocarbonyl Compounds with Aldehydes and Ketones
535(6)
Base-Promoted Reactions of XXX-Diazocarbonyl Compounds with Aldehydes: Synthesis of (N-Butoxy-carbonyl-L-Phenylalanyl)-Methyl Phenyl Ketone
537(4)
10.3 Acid-Catalyzed Reactions of XXX-Diazocarbonyl Compounds with Aldehydes
541(5)
Synthesis of XXX-Dicarbonyl Compounds via Tin(II) Chloride-Catalyzed Reaction: Conversion of Hydrocinnamaldehyde into Ethyl 3-Oxo-5-phenylvalerate
543(3)
10.4 Synthesis of Tetrahydrofurans
546(1)
Tetrahydrofuran Annulation with XXX-p-Methoxybenzyl Pivalaldehyde and Ethyl Diazoacetate: Synthesis of Substituted Tetrahydrofuran 14
548
10.5 Olefination of Aldehydes and Ketones with Diazocarbonyl Compounds
547(4)
10.6 Acid-Catalyzed Reactions of XXX-Diazocarbonyl Compounds with Ketones
551(11)
Homologation of Cyclobutanone Ring with Ethyl Diazoacetate: Synthesis of Methyl (2S, 3aR, 6aS)-1,2,3,3a,4,5,6,6a-Octahydro-2-methyl-4-oxopentalene-2-carboxylate
557(5)
10.7 References
562(6)
11. Acid-Promoted Cyclization of Unsaturated and Aromatic Diazo Ketones
568(32)
11.1 Introduction
568(1)
11.2 Cyclization of XXX, XXX-Unsaturated Diazoketones
569(6)
11.3 Cyclization of XXX, XXX-Unsaturated Diazoketones
575(8)
11.4 Intramolecular Alkylation of Diazoketones through Aryl Participation
583(8)
11.4.1 Ar(1)-5 Participation in the Cyclization of Aromatic Diazoketones
584(5)
11.4.2 Ar(1)-6 Participation in the Cyclization of Aromatic Diazoketones
589(1)
11.4.3 Ar(1)-4 Cyclization in the Cyclization of Aromatic Diazoketones
590(1)
11.5 Synthesis of Heterocycles by Acid-Promoted Cyclization of XXX-Diazocarbonyl Compounds
591(4)
11.6 References
595(5)
12. Miscellaneous Diazocarbonyl Reactions
600(41)
12.1 Introduction
600(1)
12.2 Oxidation of Diazocarbonyl Compounds
600(6)
Oxidation of N-Benzyloxycarbonyl-L-phenylalanyl diazomethane with Dimethyldioxirane. Preparation of an N-Protected Amino Glyoxal Hydrate
604(2)
12.3 XXX-Hydride Elimination
606(8)
Preparation of Methyl (Z)-2-Undecenoate from Methyl 2-Diazoundecanoate.
612(2)
12.4 X-Y Insertion Reactions
614(10)
12.4.1 X-Y = The Halogens
614(2)
12.4.2 X-Y = Arenesulfonyl Halides (ArS-X)
616(2)
12.4.3 X-Y = Areneselenyl Halides and Diphenyl Diselenide (ArSe-X)
618(1)
Preparation of 2-Phenylselenyl-2-cyclohexen-1-one from 2-Diazocyclohexanone
621
12.4.4 X-Y = Trialkylboranes (R-BR(2))
619(5)
12.5 Dimerization Reactions
624(3)
12.6 Diazocarbonyl Compounds as 1,3-Dipoles in [3+2] Cycloaddition Reactions
627(7)
12.7 References
634(7)
Index 641

An electronic version of this book is available through VitalSource.

This book is viewable on PC, Mac, iPhone, iPad, iPod Touch, and most smartphones.

By purchasing, you will be able to view this book online, as well as download it, for the chosen number of days.

Digital License

You are licensing a digital product for a set duration. Durations are set forth in the product description, with "Lifetime" typically meaning five (5) years of online access and permanent download to a supported device. All licenses are non-transferable.

More details can be found here.

A downloadable version of this book is available through the eCampus Reader or compatible Adobe readers.

Applications are available on iOS, Android, PC, Mac, and Windows Mobile platforms.

Please view the compatibility matrix prior to purchase.