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6,12‐Diphenyldibenzo[ b,f ][1,5]diazocine as an Electron‐Capture Agent: Efficient Mechanistic Probe for SET Processes and Reagent for the Oxidative Dimerization of Benzylic Organometallics
Author(s) -
Eisch John J.,
Yu Kun,
Rheingold Arnold L.
Publication year - 2012
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201200278
Subject(s) - chemistry , reagent , indole test , aromaticity , yield (engineering) , lithium (medication) , ring (chemistry) , medicinal chemistry , stereochemistry , organic chemistry , molecule , medicine , materials science , metallurgy , endocrinology
In the present study, 6,12‐diphenyldibenzo[ b , f ][1,5]diazocine, which X‐ray diffraction measurements have now shown to possess a tub‐shaped, eight‐membered central ring, has been treated with sodium or lithium metal at 25 °C in THF, in an attempt to form the planar, Hückel‐aromatic dianion by the addition of two electrons to the central diazocine. Hydrolysis of such an aromatic dianion should have led to the isomeric 5,12‐ or 5,6‐dihydro derivative of the original diazocine. In actuality, the only product obtained quantitatively upon hydrolytic workup was the interesting quadricyclic transannular reduction product, 4b,9b‐diphenyl‐4b,5,9b,10‐tetrahydroindolo[3,2‐ b ]indole, whose 3D structure has now been confirmed by X‐ray crystallography and 13 C NMR spectroscopy. Preferential SET transannular reduction of the diazocine to yield the quadricyclic indolo[3,2‐ b ]indole dianion, rather than the planar, Hückel‐aromatic anion, is ascribed to the transannular electronic stabilization operative in the tub‐shaped diazocine radical‐anion. The quantitative generation of the indolo[3,2‐ b ]indole dianion can be employed for the oxidative dimerization of the organic groups in benzylic lithium reagents. Thus treating one equivalent of the diazocine with two equivalents of benzyllithium, benzhydryllithium, or trityllithium yields quantitatively bibenzyl, 1,1,2,2‐tetraphenylethane, or (4‐benzhydrylphenyl)triphenylmethane, respectively. This oxidative dimerization is potentially of practical preparative scope, since the hydrolysis byproduct, the indolo[3,2‐ b ]indole, is conveniently reconverted into the starting diazocine reagent by oxidation with chromium trioxide in acetic acid. The formation of the indolo[3,2‐ b ]indole as a byproduct in the carbometalation of the diazocine by various RLi and Grignard reagents offers a clue as to the SET mechanism of carbometalation.