Beilstein J. Org. Chem.2013,9, 1977–2001, doi:10.3762/bjoc.9.234
are emerging as a powerful tool in amine synthesis. This article reviews synthetic applications of amine radical cations produced by visible light photocatalysis.
Keywords: α-amino radical; amine radical cation; catalysis; distonicion; free radical; iminium ion; photoredox; visible light
(distonicion) [106]. We have applied Ru(bpz)3(PF6)2-catalyzed photooxidation of N-cyclopropylanilines to induce this rearrangement reaction. The resulting distonicion was then intercepted by alkenes to produce [3 + 2] annulation products (Scheme 32) [107]. An aryl group on the amine was required for the
ring opening to release the ring strain while producing a distonicion 149 with a primary radical. Distonicion 149 is added via a Giese-type radical addition to an alkene, yielding a more stable distonicion 151 with a secondary radical. Intramolecular addition of the secondary radical to the iminium
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Graphical Abstract
Scheme 1:
Amine radical cations’ mode of reactivity.
Beilstein J. Org. Chem.2013,9, 1285–1295, doi:10.3762/bjoc.9.145
ions centered at m/z 1055 [M − 4H2O − H]− and m/z 983 [M − 8H2O − H]−.
Along with the singly charged [M − nH2O − H]− ions, six types of singly and multiply charged simple and distonicion clusters and solvent adducts were detected within m/z 1000 and m/z 3000 (Figure 1 and Table 1): [M(n) − nH2O − xH]x
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Graphical Abstract
Scheme 1:
Proposed mechanisms for the formation of fullerenol anions and distonic radical anions observed by ...