Infoscience

Journal article

Hydrazines and Azides via the Metal-Catalyzed Hydrohydrazination and Hydroazidation of Olefins

The discovery, study, and implementation of the Co- and Mn-catalyzed hydrohydrazination and hydroazidation reactions of olefins are reported. These reactions are equiv. to direct hydroaminations of C-C double bonds with protected hydrazines or hydrazoic acid but are based on a different concept in which the H and the N atoms come from two different reagents, a silane and an oxidizing nitrogen source (azodicarboxylate or sulfonyl azide). The hydrohydrazination reaction using di-tert-Bu azodicarboxylate is characterized by its ease of use, large functional group tolerance, and broad scope, including mono-, di-, tri-, and tetrasubstituted olefins. Key to the development of the hydroazidation reaction was the use of sulfonyl azides as nitrogen sources and the activating effect of tert-Bu hydroperoxide. The reaction was found to be efficient for the functionalization of mono-, di-, and trisubstituted olefins, and only a few functional groups are not tolerated. The alkyl azides obtained are versatile intermediates and can be transformed to the free amines or triazoles without isolation of the azides. Preliminary mechanistic investigations suggest a rate-limiting hydrocobaltation of the alkene, followed by an amination reaction. Radical intermediates cannot be ruled out and may be involved. [on SciFinder (R)]

    Keywords: Addition reaction (prepn. of hydrazines and azides via the metal-catalyzed hydrohydrazination and hydroazidation of olefins); Alkenes Role: RCT (Reactant) ; RACT (Reactant or reagent) (prepn. of hydrazines and azides via the metal-catalyzed hydrohydrazination and hydroazidation of olefins); Azides; Hydrazides Role: SPN (Synthetic preparation) ; PREP (Preparation) (prepn. of hydrazines and azides via the metal-catalyzed hydrohydrazination and hydroazidation of olefins) ; alkene hydroazination hydroazidation azide hydrazine prepn

    Note:

    CAN 145:396775

    21-2

    General Organic Chemistry

    Laboratorium fuer Organische Chemie,ETH Zuerich, Hoenggerberg HCI-H335,Zurich,Switz.

    Journal

    0002-7863

    written in English.

    104-51-8P (Butylbenzene); 76716-21-7P; 773882-01-2P; 773882-08-9P; 911392-13-7P Role: BYP (Byproduct), PREP (Preparation) (prepn. of hydrazines and azides via the metal-catalyzed hydrohydrazination and hydroazidation of olefins); 7646-79-9 (Cobalt chloride (CoCl2); 14167-18-1; 15684-35-2; 26490-63-1 (Cobalt tetrafluoroborate) Role: CAT (Catalyst use), USES (Uses) (prepn. of hydrazines and azides via the metal-catalyzed hydrohydrazination and hydroazidation of olefins); 10141-05-6 (Cobalt nitrate) Role: CAT (Catalyst use), RCT (Reactant), USES (Uses), RACT (Reactant or reagent) (prepn. of hydrazines and azides via the metal-catalyzed hydrohydrazination and hydroazidation of olefins); 858344-69-1DP Role: CAT (Catalyst use), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), USES (Uses), RACT (Reactant or reagent) (prepn. of hydrazines and azides via the metal-catalyzed hydrohydrazination and hydroazidation of olefins); 7440-48-4DP (Cobalt); 14324-99-3P; 866487-21-0P Role: CAT (Catalyst use), SPN (Synthetic preparation), PREP (Preparation), USES (Uses) (prepn. of hydrazines and azides via the metal-catalyzed hydrohydrazination and hydroazidation of olefins); 124-18-5 (Decane); 811-98-3 (Methanol-d4) Role: NUU (Other use, unclassified), USES (Uses) (prepn. of hydrazines and azides via the metal-catalyzed hydrohydrazination and hydroazidation of olefins); 56-45-1 (L-Serine); 62-57-7 (2-Aminoisobutyric acid); 67-64-1 (Acetone); 71-48-7 (Cobalt acetate); 79-92-5; 81-08-3; 88-15-3 (2-Acetylthiophene); 90-02-8 (Salicylaldehyde); 91-20-3 (Naphthalene); 94-59-7 (5-Allyl-1,3-benzodioxole); 95-13-6 (1H-Indene); 95-16-9 (Benzothiazole); 98-01-1 (Furfural); 98-09-9 (Benzenesulfonyl chloride); 98-59-9 (p-Toluenesulfonyl chloride); 98-68-0 (4-Methoxybenzenesulfonyl chloride); 98-74-8 (4-Nitrobenzenesulfonyl chloride); 98-83-9 (alpha-Methylstyrene); 98-86-2 (Acetophenone); 100-07-2 (4-Methoxybenzoyl chloride); 100-39-0 (Benzyl bromide); 100-42-5 (Styrene); 100-69-6 (2-Vinylpyridine); 104-93-8 (1-Methoxy-4-methylbenzene); 107-18-6 (Allyl alcohol); 109-08-0 (Methylpyrazine); 109-49-9 (5-Hexen-2-one); 110-02-1 (Thiophene); 110-83-8 (Cyclohexene); 115-19-5 (2-Methyl-3-butyn-2-ol); 123-63-7; 142-29-0 (Cyclopentene); 487-89-8 (1H-Indole-3-carboxaldehyde); 498-60-2 (3-Furancarboxaldehyde); 498-66-8 (Norbornene); 513-42-8 (Methallyl alcohol); 536-74-3 (Phenylacetylene); 556-82-1 (3-Methyl-2-buten-1-ol); 557-40-4 (Diallyl ether); 563-47-3; 563-79-1 (2,3-Dimethyl-2-butene); 583-60-8 (2-Methylcyclohexanone); 591-80-0 (4-Pentenoic acid); 593-60-2 (Vinyl bromide); 594-44-5 (Ethanesulfonyl chloride); 598-32-3 (3-Buten-2-ol); 599-04-2 (D-Pantolactone); 623-70-1; 627-26-9 (trans-Crotononitrile); 627-27-0 (3-Buten-1-ol); 638-38-0 (Manganese(II) acetate); 693-86-7 (Vinylcyclopropane); 763-29-1 (2-Methyl-1-pentene); 768-56-9 (3-Butenylbenzene); 771-98-2 (1-Phenylcyclohexene); 773-64-8 (Mesitylenesulfonyl chloride); 825-76-3 (alpha-Cyclopropylstyrene); 870-50-8 (Di-tert.-butyl azodicarboxylate); 873-66-5 (trans-beta-Methylstyrene); 931-88-4 (Cyclooctene); 939-26-4 (2-Bromomethylnaphthalene); 1003-29-8 (2-Pyrrolecarboxaldehyde); 1118-71-4 (Dipivaloylmethane); 1120-56-5 (Methylenecyclobutane); 1121-60-4 (2-Pyridinecarboxaldehyde); 1122-62-9 (2-Acetylpyridine); 1192-37-6 (Methylenecyclohexane); 1307-86-4 (Cobalt(III) hydroxide); 1499-21-4; 1520-21-4 (4-Aminostyrene); 1530-32-1; 1700-10-3 (1,3-Cyclooctadiene); 1708-29-8 (2,5-Dihydrofuran); 1730-25-2 (Allylmagnesium bromide); 1972-28-7 (Diethyl azodicarboxylate); 2344-80-1; 3060-50-2 (alpha,alpha-Diphenylglycine); 3070-53-9 (1,6-Heptadiene); 3195-24-2 (Diethyl diallylmalonate); 3770-50-1 (Ethyl 1H-indole-2-carboxylate); 4407-36-7 (trans-Cinnamyl alcohol); 4552-50-5; 4894-61-5 (trans-Crotyl chloride); 5162-44-7 (1-Bromo-3-butene); 5674-01-1 (Methallylmagnesium chloride); 6044-68-4 (Acrolein dimethylacetal); 6117-91-5 (2-Buten-1-ol); 6142-73-0 (Methylidenecyclopropane); 13269-52-8 (trans-3-Hexene); 13750-81-7 (1-Methyl-1H-imidazole-2-carboxaldehyde); 14593- 3-2 (Allyl benzyl ether); 23378-88-3; 28920-43-6; 37942-07-7; 858344-71-5 Role: RCT (Reactant), RACT (Reactant or reagent) (prepn. of hydrazines and azides via the metal-catalyzed hydrohydrazination and hydroazidation of olefins); 127-91-3P; 493-03-8P; 690-94-8P; 769-57-3P (2-Methyl-3-phenyl-2-butene); 1487-18-9P (2-Vinylfuran); 1674-10-8P (1,2-Dimethylcyclohexene); 1918-82-7P (2-Vinylthiophene); 2433-66-1P (2-Vinylpyrrole); 2489-89-6P (2-(But-3-en-1-yl)naphthalene); 3240-29-7P (3-Butenoylbenzene); 4129-17-3P; 4177-16-6P (Vinylpyrazine); 4547-62-0P (4-Nitrobenzenesulfonyl azide); 4547-64-2P (4-Methoxybenzenesulfonyl azide); 5402-29-9P (1,2-Dimethylcyclohexanol); 5658-46-8P; 6515-13-5P (2-Isopropenylpyridine); 6683-51-8P (3-Methyl-3-buten-1-ylbenzene); 16975-71-6P (1-Methyl-2-vinyl-1H-imidazole); 17618-94-9P (2-(1-Propen-1-yl)pyridine); 19005-93-7P (1H-Indole-2-carboxaldehyde); 26638-43-7P (Methyl 2-chlorosulfonylbenzoate); 30616-73-0P (2-Isopropenylthiophene); 50361-91-6P; 50562-79-3P; 53654-35-6P (2-Vinyl-1H-indole); 57476-50-3P (1-tert.-Butoxycarbonyl-1H-indole-3-carboxaldehyde); 65037-62-9P; 66580-25-4P (2-Dimethylaminoethylpyrazine); 66730-39-0P (2-Isopropenylbenzothiazole); 67364-02-7P (3-Vinylfuran); 71293-01-1P; 72485-49-5P; 88040-86-2P (2-Methoxy-5-methylbenzenesulfonyl chloride); 102619-05-6P; 105966-43-6P; 113882-48-7P (Benzyl 4-pentenoate); 126983-27-5P; 131124-21-5P; 135006-32-5P; 136787-49-0P (Allyloxy-tert.-butyldiphenylsilane); 157835-85-3P; 161282-57-1P; 171895-06-0P; 180283-59-4P; 188263-82-3P; 704900-21-0P; 858344-69-1P; 866487-22-1P; 911391-75-8P; 911391-84-9P; 911392-12-6P; 911392-15-9P; 911392-16-0P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. of hydrazines and azides via the metal-catalyzed hydrohydrazination and hydroazidation of olefins); 694-53-1 (Phenylsilane); 1761-56-4; 3277-26-7; 18164-03-9; 30110-74-8; 69698-15-3; 151930-49-3; 911391-71-4; 911391-72-5; 911391-73-6; 911392-00-2 (2-Methoxy-4-methylbenzenesulfonyl azide); 911392-01-3 (2-Methoxycarbonylbenzenesulfonyl azide) Role: RGT (Reagent), RACT (Reactant or reagent) (prepn. of hydrazines and azides via the metal-catalyzed hydrohydrazination and hydroazidation of olefins); 938-10-3P (Phenylsulfonyl azide); 941-55-9P (p-Toluenesulfonyl azide); 1516-70-7P (Methanesulfonyl azide); 24906-63-6P (2,4,6-Trimethylbenzenesulfonyl azide); 70284-09-2P (Ethanesulfonyl azide) Role: RGT (Reagent), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. of hydrazines and azides via the metal-catalyzed hydrohydrazination and hydroazidation of olefins); 16466-61-8P; 22374-89-6P (4-Phenyl-2-butanamine); 26178-34-7P; 32366-28-2P; 33794-96-6P (Azidocyclooctane); 58977-25-6P; 73839-93-7P; 88887-87-0P (1-Methyl-1-cyclopropanamine hydrochloride); 126745-48-0P; 166327-12-4P (2-Azido-4-phenylbutane); 174886-05-6P (1-Methyl-1-cyclobutanamine hydrochloride); 180137-93-3P; 221313-63-9P; 345210-67-5P; 475152-60-4P; 704899-84-3P; 704899-87-6P; 704899-91-2P; 704899-94-5P; 704899-98-9P; 704900-03-8P; 704900-06-1P; 704900-09-4P; 704900-15-2P; 704900-18-5P; 704900-24-3P; 704900-28-7P; 704900-40-3P; 704900-42-5P; 704900-44-7P; 704900-46-9P; 704900-48-1P; 704900-51-6P; 704900-57-2P; 704900-57-2P; 773882-02-3P; 773882-03-4P; 773882-04-5P; 773882-05-6P; 773882-06-7P; 773882-07-8P; 858344-60-2P; 858344-61-3P; 858344-62-4P; 858344-63-5P; 858344-64-6P; 858344-65-7P; 858344-66-8P; 858344-67-9P; 858344-68-0P; 858344-70-4P; 911391-70-3P; 911391-74-7P; 911391-76-9P; 911391-77-0P; 911391-78-1P; 911391-79-2P; 911391-80-5P; 911391-81-6P; 911391-82-7P; 911391-83-8P; 911391-85-0P; 911391-86-1P; 911391-87-2P; 911391-88-3P; 911391-89-4P; 911391-90-7P; 911391-91-8P; 911391-92-9P; 911391-93-0P; 911391-94-1P; 911391-96-3P; 911391-98-5P; 911391-99-6P; 911392-02-4P; 911392-03-5P; 911392-04-6P; 911392-05-7P; 911392-06-8P; 911392-07-9P; 911392-08-0P; 911392-09-1P; 911392-10-4P; 911392-11-5P; 911392-14-8P; 911392-17-1P; 911392-18-2P; 911392-19-3P; 911392-20-6P; 911392-21-7P Role: SPN (Synthetic prepa ation), PREP (Preparation) (prepn. of hydrazines and azides via the metal-catalyzed hydrohydrazination and hydroazidation of olefins)

    Reference

    Record created on 2007-12-17, modified on 2016-08-08

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