Carbethoxynitrene by α-Elimination. Reactions with Hydrocarbons<sup>1,2</sup>

Lwowski, Walter; Maricich, Tom J.

doi:10.1021/ja01094a018

Cited by 169 publications

(63 citation statements)

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“…The results are recorded in Table 3. The main feature is the nearly identical ratio of insertion (16) to addition (15): 0.15 with 2a, 0.17 with 18 (8). This ratio is close to that observed in the electrochemical reduction of NFU in acetonitrile in the presence of cyclohexene: 16/15 = 0.1 I.…”

Section: ) Smithsupporting

confidence: 77%

“…[7]), and not the N-H bond of NFU (eq. [8]), is reduced. This is confirmed by the absence of hydrogen evolution during the preparative electrolysis of NFU on mercury [8] EtOCONHF + e + E~OCONF + f H2 20 and on platinum.…”

Section: Voltammettymentioning

confidence: 96%

“…[8]), is reduced. This is confirmed by the absence of hydrogen evolution during the preparative electrolysis of NFU on mercury [8] EtOCONHF + e + E~OCONF + f H2 20 and on platinum. Thus although ( i ) NFU (pK., = 5.69 in water) is more acidic than NCU (pK, = 8.02) (3), and (ii) an N-F bond is more difficult to reduce than an N-Cl bond, the reduction of NFU involves the cleavage of the N-halogen bond (eqs.…”

Section: Voltammettymentioning

confidence: 96%

“…The organic phases were dried and the solvent was evaporated. The ' H nmr spectrum of the crude product showed the presence of urethan (4), oxadiazole (8), and diethyl hydrazodicarboxylate (9). The yields determined by vpc (0s-138, 15%) are given in Table 2, entry I.…”

Section: Rencriorzs With Onsesmentioning

confidence: 99%

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The electrochemical reduction of N-fluorourethans in acetonitrile. The generation of carbethoxynitrene

Lessard¹,

Bérubé²

1984

Can. J. Chem.

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The electrochemical reduction of N-fluoro-N-methylurethan ( l a ) and N-fluorourethan (2tr) in acctonitrile gcnerates the amidc anion and a fluoride ion. Both the fluoride and thc amide anion can rcact with the starting N-fluoroamidc cither as bascs or as nucleophilcs. Many products are formcd and the coulonictric results are low (0.5 to 0.7 F/rnol). In thc case of NFU (2g), abstraction of the proton on nitrogen both by the urethan anion and the fluoridc anion generatcs thc conjugate base EtOCONF (7) which immediatcly undergoes a-elimination of the fluoride ion to givc carbethoxynitrene (11). This nitrcne was gencpted also by treating NFU (20) with a base such as tricthylamjne or lithium hydride. The a-elimination of F From EtOCONF is much casier than the a-elimination of Cl-from EtOCONCI.JEAN LESSARD et DENIS BERUBE. Can. J. Chcm. 62. 768 (1984).La rkduction Clcctrochimique du N-fluoro-N-mkthylurithane (In) ct du N-fluorourkthanc (20) conduit $

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Section: ) Smithsupporting

confidence: 77%

Section: Voltammettymentioning

confidence: 96%

Section: Voltammettymentioning

confidence: 96%

Section: Rencriorzs With Onsesmentioning

confidence: 99%

See 2 more Smart Citations

The electrochemical reduction of N-fluorourethans in acetonitrile. The generation of carbethoxynitrene

Lessard¹,

Bérubé²

1984

Can. J. Chem.

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“…In the fields infancy, azides were decomposed thermally or photochemically to produce nitrenes; however, such strategies were unselective and low-yielding. [28] An improved protocol can be realised by rhodium-mediated decomposition of azides to form metallonitrenoids. Driver and coworkers used this approach to synthesize indoles 38 by a di-A C H T U N G T R E N N U N G rhodium(II)-catalyzed intramolecular CÀH amination from the decomposition of azidoacrylates 37 (Scheme 14).…”

Section: Nitrogen Heterocycles By C à H Aminationmentioning

confidence: 99%