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A C(sp 2 )−H Dehydrogenation of Heteroarenes and Arenes by a Functionalized Aluminum Hydride
Author(s) -
Chen Shimin,
Li Bin,
Wang Xiaoping,
Huang Yanting,
Li Jiancheng,
Zhu Hongping,
Zhao Lili,
Frenking Gernot,
Roesky Herbert W.
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201703804
Subject(s) - chemistry , intramolecular force , dehydrogenation , yield (engineering) , medicinal chemistry , acceptor , naphthalene , hydride , photochemistry , metal , catalysis , stereochemistry , organic chemistry , materials science , physics , metallurgy , condensed matter physics
The 2‐aminophenylaluminum dihydride (2‐TMP‐C 6 H 4 )AlH 2 ( 2 ) has been prepared and characterized for the first time. Compound 2 features an intramolecular N⋅⋅⋅Al donor–acceptor bond. 2 reacted with N ‐methylpyrrole and N ‐methylindole (both at 50 °C) by means of the elusive AlH C(sp 2 )−H dehydroalumination to aluminum heteroaryls ( 3 and 4 ). Moreover, 2 reacted with PhCCSiMe 3 (at room temperature) and Ph 2 CCNR (R= i Pr or 2,6‐ i Pr 2 C 6 H 3 , at −30 to 20 °C ) to yield aluminaindene heterocycle ( 8 ) and alumina‐aza‐naphthalene heterocycle ( 9 and 10 ), respectively. These reactions underwent hydroalumination followed by AlH C(sp 2 )−H dehydroalumination. The reaction mechanism has been studied by combining experiment and quantum chemical calculations, with the result that the key heteroarene or arene C(sp 2 )−H bond activation is involved under cooperative interaction by the inherent N/Al donor/acceptor pair. The reported reactions open a straightforward route to heteroaryl and unique heterocyclic aluminum compounds.