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

by Doyle, Michael P.; McKervey, M. Anthony; Ye, Tao

• ISBN13: 9780471135562
• ISBN10: 0471135569
• Edition: 1st
• Format: Hardcover
• Copyright: 1998-01-19
• Publisher: Wiley-Interscience

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