Reductive Cyclopropanations Catalyzed by Dinuclear Nickel Complexes
Dinuclear Ni complexes supported by naphthyridine-diimine (NDI) ligands catalyze the reductive cyclopropanation of alkenes with CH2Cl2 as the methylene source. The use of mild terminal reductants (Zn or Et2Zn) confers significant functional-group tolerance, and the catalyst accommodates structurally and electronically diverse alkenes. Mononickel catalysts bearing related N chelates afford comparatively low cyclopropane yields (≤20 %). These results constitute an entry into catalytic carbene transformations from oxidized methylene precursors.
Zhou, You-Yun,Uyeda, Christopher
supporting information
p. 3171 - 3175
(2016/03/12)
Aluminum chloride catalyzed hydrosilylation of cyclopropanes with chlorodimethylsilane
Aluminum chloride can be utilized as an active catalyst for the highly regioselective hydrosilylation of 1-alkyl, 1-aryl, 1,1-dialkyl, and cyclic cyclopropanes with chlorodimethylsilane in hexane at room temperature.
Pyrolysis of Alkyl Acetates. A Radical Pathway for the Formation of Minor Products
Decyl acetate and decene pyrolysis under the same reaction conditions show that the formation of the minor products during the pyrolysis of esters occurs by a parallel, and not a secondary, reaction.The radioactivity observed in the CO2 and CO produced during the pyrolysis of 1-hexyl acetate-1-14C and the radioactivity in the methane from the pyrolysis of 1-hexyl acetate-2-14C strongly suggested a radical reaction pathway for the formation of the minor products.Considering the above results together with the radioactivity data of gas samples from the pyrolysis of 1-decyl-1-14C acetate, 1-hexyl-1-14C acetate, and 1-heptadecyl-1-14C acetate leads to the conclusion that the mechanism of pyrolysis of esters may be viewed as a cyclo-DEDNAN mechanism for the formation of the major alkene product and a radical mechanism for the formation of minor products.A useful synthetic procedure for the preparation of high carbon number alkenes (>10) also results from this study.
Shi, Buchang,Ji, Ying,Dabbagh, Hossein A.,Davis, Burtron H.
p. 845 - 849
(2007/10/02)
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