Metal-mediated oxidative amination of hydrocarbons
- Tufts Univ., Medford, MA (United States)
Two routes to high-valent imidometal species capable of transferring the nitrene functionality into hydrocarbon substrates have been examined. Transfer of the NH group from 1-aminopyridinium iodide to certain olefins in the presence of base and FeCl(TPP) forms the corresponding aziridine. This systems also aminates ethylbenzene. The three component systems RNH{sub 2}/PhI(OAc){sub 2}/MnCl(TPP) (R=Me,C{sub 6}H{sub 11}, Bu) aminate cyclohexane, ethylbenzene and several olefins. The system with R-Bu yields a high-valent Mn intermediate, tentatively identified as Mn(NBu)(TPP)Cl, which decomposes to Mn(III) over several hours in solution. In this system evidence for a metal-independent for a metal-independent amination pathway has also be obtained. For R=Me, C{sub 6}H{sub 11}, a novel C-N bond cleavage process, resulting in the known complex MnN(TPP), apparently competes with substrate amination. The results are consistent with stabilization of reactive Mn(NR)(TPP)Cl either via transfer of NR or formal elimination of RC.
- OSTI ID:
- 141112
- Report Number(s):
- CONF-930304-; TRN: 93:003688-0787
- Resource Relation:
- Conference: 205. American Chemical Society national meeting, Denver, CO (United States), 28 Mar - 2 Apr 1993; Other Information: PBD: 1993; Related Information: Is Part Of 205th ACS national meeting; PB: 1951 p.
- Country of Publication:
- United States
- Language:
- English
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