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Evidence for a stereospecific 1,2-elimination reaction in a 1,1-diazene. Synthesis and decomposition of [N-phenyl(threo- and erythro)-2-deuterio-1-methylpropyl)amino]nitrene

Duan, Daniel C. and Dervan, Peter B. (1983) Evidence for a stereospecific 1,2-elimination reaction in a 1,1-diazene. Synthesis and decomposition of [N-phenyl(threo- and erythro)-2-deuterio-1-methylpropyl)amino]nitrene. Journal of Organic Chemistry, 48 (7). pp. 970-976. ISSN 0022-3263. https://resolver.caltech.edu/CaltechAUTHORS:20160511-153523456

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Abstract

The mechanism of the formal 1,2-elimination reaction of 1,1-diazenes to alkenes is examined. The syntheses and decompositions of [N-phenyl(1-methylpropy1)aminolnitrene (6), [N-phenyl(erythro-2-deuterio-l-methylpropy1)aminolnitrene (7), and [N-phenyl(threo-2-deuteri~l-methylpropyl)amino]nitrene (8) are reported. Oxidation of 1-(1-methylpropy1)-1-phenylhydrazine (9) with nickel peroxide at 100 °C affords 1-butene, trans-2-butene, cis-2-butene, butane, and benzene in ratios of 0.59:0.300.097:0.005:1.00. Reaction of the corresponding benzenesulfonamide 10 with base at 100 “C affords similar ratios. Oxidation of l-(erythro-2-deuterio-l-methylpropyl)-1-phenylhydrazine (14) at 100 °C affords 1-butene, trans-2-butene (100 ± 2% d_1), cis-2-butene (2.8 ± 2% d_1), and butane in ratios of 0.67:0.30:0.03:0.004. Oxidation of l-(threo-2-deuterio-l-methylpropyl)-lphenylhydrazine (20) at 100 °C affords 1-butene, trans-2-butene (1.8 ± 2% d_l), cis-2-butene (97.9 ± 2% d_1), and butane in ratios of 0.77:0.11:0.11:0.009. Reaction of the corresponding benzenesulfonamides 15 and 21 with base at 100 °C affords similar results. Primary kinetic isotope effects for 2-butene formation from the erythroand threo-1,l-diazene diastereomers were 3.5 and 3.4. respectively. The 1,l-diazene 1,2-elimination reaction studied here is a stereospecific cis-elimination process.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jo00155a008DOIArticle
http://pubs.acs.org/doi/abs/10.1021/jo00155a008PublisherArticle
ORCID:
AuthorORCID
Dervan, Peter B.0000-0001-8852-7306
Additional Information:© 1983 American Chemical Society. Received August 23, 1982. We are grateful to the National Science Foundation for support (CHE80-06495) of this research and use of the Southern California NMR Facility supported by NSF Grant CHE79-16324. [D.C.D] National Science Foundation Predoctoral Fellow, 1976-1979. [P.B.D] Camille and Henry Dreyfus Teacher-Scholar, 1978-1983.
Funders:
Funding AgencyGrant Number
NSFCHE80-06495
NSFCHE79-16324
NSF Predoctoral FellowshipUNSPECIFIED
Camille and Henry Dreyfus FoundationUNSPECIFIED
Issue or Number:7
Record Number:CaltechAUTHORS:20160511-153523456
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160511-153523456
Official Citation:Evidence for a stereospecific 1,2-elimination reaction in a 1,1-diazene. Synthesis and decomposition of [N-phenyl(threo- and erythro)-2-deuterio-1-methylpropyl)amino]nitrene Daniel C. Duan and Peter B. Dervan The Journal of Organic Chemistry 1983 48 (7), 970-976 DOI: 10.1021/jo00155a008
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:67028
Collection:CaltechAUTHORS
Deposited By: Victoria Brennan
Deposited On:20 May 2016 00:00
Last Modified:26 Nov 2019 11:15

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