Organic Reactions, Volume 66

by Overman, Larry E.

• ISBN13: 9780471682585
• ISBN10: 0471682586
• Edition: 1st
• Format: Hardcover
• Copyright: 2005-09-12
• Publisher: Wiley

Summary

Organic Reactions is a comprehensive series of volumes composed of chapters devoted to important synthetic reactions. For each volume, the chapter authors are world-renowned experts with extensive hands-on experience in the field. The chemistry is presented from a preparative point of view and particular attention is given to reaction limitations, interfering influences, effects of chemical structure, and the selection of experimental conditions. * Each reaction is fully referenced to the primary literature * Numerous detailed procedures illustrate the significant modifications of each method * Includes tables that contain all possible examples of the reaction under consideration

Author Biography

Larry Overman, current editor-in-chief for the Organic Reactions series, is Professor at the University of California at Irvine.

Table of Contents

The Allylic Trihaloacetimidate Rearrangement	1	(108)
Larry E. Overman
Nancy E. Carpenter
Acknowledgments	3	(1)
Introduction	3	(1)
Mechanism	4	(5)
Thermal Rearrangements	4	(2)
Metal-Catalyzed Rearrangements	6	(3)
Scope & Limitations	9	(24)
Preparation and Stability of Allylic Trihaloacetimidates	9	(1)
Preparation of Allylic Trichloroacetimidates	9	(1)
Preparation of Allylic Trifluoroacetimidates	10	(1)
Stability of Allylic Trihaloacetimidates	11	(1)
Thermal Rearrangements of Allylic Trihaloacetimidates	12	(1)
Reaction Conditions: Temperature, Solvent, and Additives	12	(2)
Scope	14	(1)
The Halogen Substituents	15	(1)
Carbon Skeleton	16	(2)
Cyclic Substrates	18	(2)
Substituent Effects and Problematic Substituents	20	(2)
Regioselectivity	22	(1)
Stereochemistry	22	(1)
Chiral Secondary Imidates: Chirality Transfer	22	(1)
Diastereoselectivity Arising from Stereocenters Outside the Pericyclic Arena	23	(1)
Geometry of the New Double Bond	24	(1)
Catalyzed Rearrangements of Allylic Trihaloacetimidates	25	(1)
General Conditions	26	(1)
Scope	27	(2)
Stereoselectivity	29	(1)
Chiral Secondary Imidates: Chirality Transfer	29	(1)
Chiral Primary Imidates: Diastereoselectivity	29	(2)
Asymmetric Catalysis	31	(2)
Applications to Synthesis	33	(8)
Overview	33	(1)
Preparation of Allylic Amines	33	(5)
Other Direct Uses of Allylic Trihaloacetamides	38	(1)
Applications in the Total Synthesis of Natural Products	39	(1)
(±)-Acivicin	39	(1)
(±)-Lactacystin	40	(1)
(±)-Pancratistatin	40	(1)
Comparison with Other Methods	41	(4)
Other Allylic Rearrangements	41	(2)
Other Routes to Allylic Amines	43	(1)
Amination of Allylic Electrophiles	43	(1)
C-H Activation	44	(1)
Hydroamination	44	(1)
Addition of Vinyl Nucleophiles to Imine Derivatives	45	(1)
Experimental Conditions	45	(2)
General Comments	45	(1)
Preparation of Allylic Trichloroacetimidates	45	(1)
Preparation of Allylic Trifluoroacetimidates	46	(1)
Thermal Rearrangements of Allylic Trihaloacetimidates	46	(1)
Metal-Catalyzed Rearrangements of Allylic Trihaloacetimidates	47	(1)
Experimental Procedures	47	(4)
2,2,2-Trichloro-N-(3,7-dimethylocta-1,6-dien-3-yl)acetamide (Alkoxide-Catalyzed Procedure for Preparing Allylic Trichloroacetimidates and Thermal Rearrangement of the Crude Imidate Intermediate)	48	(1)
3,7-Dimethylocta-1,6-dien-3-amine (Basic Hydrolysis of an Allylic Trichloroacetamide to Form the Allylic Amine)	48	(1)
(Z)-2-[(6S)-6-(2,2-Dimethyl-1,3-dioxolan-4-yl)-4-methylcyclohex-3-enylidene]ethyl 2,2,2-Trichloroacetimidate (Preparation of a Trichloroacetimidate Using DBU)	48	(1)
2,2,2-Trichloro-N-[(1R,6S)-6-(2,2-dimethyl-1,3-dioxolan-4-yl)-4-methyl-1-vinylcyclohex-3-enyl]acetamide (Thermal Rearrangement of a Trichloroacetimidate in the Presence of K2CO3)	48	(1)
(4S,5S)-4-(tert-Butyldimethylsiloxymethyl)-5-[(3S,4S,1E)-4-tert-butyldiphenylsiloxy-3-(2,2,2-trifluoroacetimidoyloxy)pentenyl]-2,2-dimethyl-1,3-dioxolane (Preparation of an Allylic Trifluoroacetimidate)	49	(1)
(4S,5S)-4-(tert-Butyldimethylsiloxymethyl)-5-[(1R,4S,2E)-4-tert-butyldiphenylsiloxy-1-(2,2,2-trifluoroacetylamino)pent-2-enyl]-2,2-dimethyl-1,3-dioxolane (Thermal Rearrangement of an Allylic Trifluoroacetimidate)	50	(1)
Cinnamyl 2,2,2-Trifluoroacetimidate (``One-Pot'' Procedure for the Preparation of an Allylic Trifluoroacetimidate)	50	(1)
(3R,4S)-4-tert-Butoxycarbonylamino-3-(trichloroacetylamino)-1-pentene (Pd(II)-Catalyzed Rearrangement of an Allylic Trichloroacetimidate)	51	(1)
(S)-2,2,2-Trichloro-N-(1-propylallyl)acetamide (Catalytic Asymmetric Rearrangement of an Allylic Trichloroacetimidate)	51	(1)
Tabular Survey	51	(52)
Catalysts Used in Table 4	53	(1)
Table 1. Rearrangements of Trihaloacetimidates of Primary Allylic Alcohols	54	(16)
Table 2A. Rearrangements of Trihaloacetimidates of Acyclic Secondary Allylic Alcohols	70	(17)
Table 2B. Rearrangements of Trihaloacetimidates of Cyclic Secondary Allylic Alcohols	87	(8)
Table 3. Rearrangements of Trihaloacetimidates of Tertiary Allylic Alcohols	95	(2)
Table 4. Transition-Metal-Catalyzed Asymmetric Rearrangements of Allylic Trihaloacetimidates	97	(6)
References	103	(6)
Asymmetric Dihydroxylation of Alkenes	109	(518)
Mark C. Noe
Michael A. Letavic
Sheri L. Snow
Stuart W. McCombie
Acknowledgments	111	(1)
Introduction	111	(2)
Mechanism and Stereochemistry	113	(7)
Scope and Limitations	120	(44)
Terminal Alkenes	120	(7)
Disubstituted Alkenes	127	(1)
1,1-Disubstituted Alkenes	127	(5)
E-1,2-Disubstituted Alkenes	132	(10)
Z-1,2-Disubstituted Alkenes	142	(2)
Trisubstituted Alkenes	144	(2)
Acyclic Trisubstituted Alkenes	146	(1)
Exocyclic Trisubstituted Alkenes	147	(1)
Endocyclic Trisubstituted Alkenes	148	(3)
Tetrasubstituted Alkenes	151	(1)
Polyalkene Substrates	152	(8)
Kinetic Resolutions	160	(2)
Functional Group Compatibility	162	(2)
Experimental Conditions	164	(20)
Stoichiometric Enantioselective Dihydroxylation Using Chiral Diamine Ligands	165	(1)
Selection of Ligand	165	(1)
Solvent, Temperature, and Concentration	165	(1)
Recovery of Ligand and Osmium	165	(1)
Catalytic Enantioselective Dihydroxylation Using Cinchona Alkaloid Ligands	166	(1)
Selection of Ligand	166	(5)
Solid-Supported Cinchona Alkaloid Catalysts	171	(5)
Osmium Sources	176	(1)
Secondary Oxidants	177	(5)
Solvent and Concentration	182	(1)
Reaction Temperature and Catalyst Loading	183	(1)
Premixed Reagents for Catalytic Enantioselective Dihydroxylation	183	(1)
Experimental Procedures	184	(14)
Procedures for the Synthesis of Ligands for Enantioselective Dihydroxylation	184	(1)
(1R,2R)-N,N'-Bis(3,3-dimethylbutyl)cyclohexane-1,2-diamine	184	(1)
1,4-Bis(9-O-dihydroquinidyl)-6,7-diphenylphthalazine [(DHQD)2DP-PHAL]	184	(1)
1,4-Bis(9-O-dihydroquinyl)-6,7-diphenylphthalazine [(DHQ)2DP-PHAL]	185	(1)
5,8-Bis(9-O-dihydroquinidyl)-2,3-diphenylpyrazino[2,3-d]pyridazine [(DHQD)2DPP]	185	(1)
5,8-Bis(9-O-dihydroquinyl)-2,3-diphenylpyrazino[2,3-d]pyridazine [(DHQ)2DPP]	186	(1)
1,4-Bis[O-6'-(4-heptyl)hydrocupreidyl]naphthopyridazine	187	(1)
3,6-Bis(hydroquinidyl)pyridazine-mono-9-anthracenylmethyl Chloride	187	(1)
6-Dihydroquinidyl-3-[1(S)-anthracen-1-yl-2,2-dimethylpropoxy]pyridazine [DHQD-PYDZ-(S)-Anthryl Ligand]	188	(1)
2,5-Diphenyl-bis(9-O-dihydroquinidyl)pyrimidine [(DHQD)2PYR]	189	(1)
2,5-Diphenyl-4,6-bis(dihydroquinyl)pyrimidine [(DHQ)2PYR]	189	(1)
1,4-Bis(dihydroquinidyl)benzo[g]phthalazine-5,10-dione [(DHQD)2AQN]	190	(1)
1,4-Bis(dihydroquinyl)benzo[g]phthalazine-5,10-dione [(DHQ)2AQN]	190	(1)
(DHQD)2PHAL---EGDMA---HEMA Block Copolymer Ligand	191	(1)
Procedures for the Enantioselective Dihydroxylation of Alkenes	191	(1)
S,S-Diethyl Tartrate [Stoichiometric Enantioselective Dihydroxylation Using a Chiral 1,2-Diamine Ligand]	191	(1)
2-(2'-Isopropoxy-3'-methoxyphenyl)-2-hydroxyethanol [Catalytic Asymmetric Dihydroxylation Using NMO as the Secondary Oxidant]	192	(1)
(R,R)-(+)-1,2-Diphenyl-1,2-ethanediol [Solid to Solid Asymmetric Dihydroxylation with NMO]	192	(1)
Buffered Asymmetric Dihydroxylation Protocol	193	(1)
General Procedure for the Asymmetric Dihydroxylation of Allylic 4-Methoxybenzoates	193	(1)
(R)-(-)-1-Phenyl-2-propen-1-yl 4-Methoxybenzoate [Kinetic Resolution]	194	(1)
(10R)-10,11-Dihydroxy-10,11-dihydrofarnesyl Acetate [Asymmetric Dihydroxylation of Non-Conjugated Polyalkenes]	194	(1)
2-Phenyl-1,2-propanediol [Asymmetric Dihydroxylation under Atmospheric Oxygen Pressure]	195	(1)
(4S)-4-Ethyl-4-hydroxy-8-methoxy-1,4-dihydropyrano[3,4-c]pyridin-3-one [Asymmetric Dihydroxylation of Enol Ethers]	195	(1)
(1R,2R)-1,2-Diphenyl-1,2-ethanediol [Asymmetric Dihydroxylation with Iodine as Secondary Oxidant]	196	(1)
(1R,2R)-1,2-Diphenyl-1,2-ethanediol [Electrochemical Asymmetric Dihydroxylation]	196	(1)
Asymmetric Dihydroxylation Using ABS-MC OsO4	197	(1)
Preparation of ABS-MC OsO4	197	(1)
(R)-1-Phenyl-1,2-ethanediol [Asymmetric Dihydroxylation Using a Polymer Bound Ligand]	197	(1)
(2R,3aR,4R,5R,7aR)-2-Phenyl-3a,4,5,7a-tetrahydrobenzo[1,3]dioxole 4,5-Diacetate [Asymmetric Dihydroxylation Using AD-mix]	198	(1)
Tabular Survey	198	(411)
Chart 1. Ligands Used in Tables 1--9	200	(9)
Chart 2. Ligands and Additives Used in Table 10	209	(5)
Table 1. Reactions of Terminal Alkenes	214	(71)
Table 2. Reactions of 1,1-Disubstituted Alkenes	285	(25)
Table 3. Reactions of Trans 1,2-Disubstituted Alkenes	310	(114)
Table 4. Reactions of Cis 1,2-Disubstituted Alkenes	424	(20)
Table 5. Reactions of Trisubstituted Alkenes	444	(39)
Table 6. Reactions of Tetrasubstituted Alkenes	483	(9)
Table 7. Reactions of Conjugated Polyalkenes	492	(17)
Table 8. Reactions of Unconjugated Polyalkenes	509	(31)
Table 9. Kinetic Resolutions	540	(4)
Table 10. Supplemental Table Entries: 2001-2004	544	(13)
Table 10A. Reactions of Terminal Alkenes	557	(6)
Table 10B. Reactions of 1,1-Disubstituted Alkenes	563	(1)
Table 10C. Reactions of Trans 1,2-Disubstituted Alkenes	564	(25)
Table 10D. Reactions of Cis 1,2-Disubstituted Alkenes	589	(3)
Table 10E. Reactions of Trisubstituted Alkenes	592	(8)
Table 10F. Reactions of Conjugated Polyalkenes	600	(2)
Table 10G. Reactions of Unconjugated Polyalkenes	602	(5)
Table 10H. Reactions of Allenes	607	(1)
Table 10I. Kinetic Resolutions	608	(1)
References	609	(18)
Cumulative Chapter Titles by Volume	627	(14)
Author Index, Volumes 1--66	641	(4)
Chapter and Topic Index, Volumes 1--66	645