Nickel-catalyzed reactions of 3,4-benzo-1,1,2,2-tetraethyl-1,2-disilacyclobut-3-ene with carbonyl compounds

Ishikawa, Mitsuo; Naka, Akinobu; Okazaki, S.; Sakamoto, H.

doi:10.1021/om00025a018

Cited by 31 publications

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“…Cyclic bis(silyl)nickel complexes have been implicated as important intermediates in the nickel-catalyzed double silylation of arenes, 3 alkynes, 4 alkenes 5 and aldehydes. 6 However, the intermediates have not been isolated due to their instability. We now describe (i) the isolation of the reactive intermediate cyclic bis The 1 H, 13 C, 31 P and 29 Si NMR spectra for 2 support the proposed structure.…”

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confidence: 99%

Stable bis(silyl)nickel complexes with o-carboranyl unit: a facile double silylation of alkynes and alkenes

Kang¹,

Kang²,

Ko³

et al. 1998

Chem. Commun.

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confidence: 99%

Stable bis(silyl)nickel complexes with o-carboranyl unit: a facile double silylation of alkynes and alkenes

Kang¹,

Kang²,

Ko³

et al. 1998

Chem. Commun.

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“…Compounds 8, 9, and 11 were isolated by MPLC. All spectral data for 8, 9, and 11 8 were identical with those of the authentic samples.…”

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confidence: 64%

Nickel-Catalyzed Reactions of Benzo[1,2:4,5]bis(1,1,2,2-tetraethyl-1,2-disilacyclobut-3-ene) with Alkynes and Ketones

et al. 1999

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Heating a benzene solution of benzo [1,2:4,5]bis(1,1,2,2-tetraethyl-1,2-disilacyclobut-3-ene) (1) with a catalytic amount of tetrakis(triethylphosphine)nickel(0) gave two regioisomers, 2 and 3, arising from C-H bond activation of benzene in 81% combined yield. The reaction of 1 with diphenylacetylene in the presence of the nickel catalyst afforded benzo[1,2:4,5]bis-(1,1,4,4-tetraethyl-2,3-diphenyl-1,4-disilacyclohexa-2,5-diene) in 91% yield, while with 3-hexyne, 1 yielded benzo[1,2:4,5]bis(1,1,2,3,4,4-hexaethyl-1,4-disilacyclohexa-2,5-diene) and its isomer (7) in 64% and 25% yields, respectively. The nickel-catalyzed reaction of 1 with benzophenone gave benzo[1,2](1,1,3,3-tetraethyl-2-oxa-1,3-disilacyclopent-4-ene) [4,5](1,1,3,3-tetraethyl-2,2-diphenyl-1,3-disilacyclopent-4-ene) and siloxane (8) in 40% and 50% yields. Similarly, with 4,4′-dimethylbenzophenone, 1 produced benzo [1,2](1,1,3,3-tetraethyl-2-oxa-1,3-disilacyclopent-4-ene) [4,5](1,1,3,3-tetraethyl-2,2-(p-tolyl)-1,3-disilacyclopent-4-ene) in 19% yield, together with a 50% yield of 8. When the similar treatment of 1 with benzophenone was carried out in cyclohexene, 7,7-diphenylnorcarane was obtained in 14% yield, along with a 54% yield of 8.

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“…GC–MS analysis of the mixture gave evidence of five products. Three peaks eluting at 16.38, 16.51, and 16.81 min were identified as a mixture of the cyclohexene-trapped diphenylcarbene isomers in a 7.4:2.4:1 ratio, 1,1′-(1-cyclohexen-1-ylmethylene)bis-benzene ( A ) (CAS 83605-32-7), 1,1′-(cyclohexylidenemethylene)bis-benzene ( B ) (CAS 30125-24-7), and 7,7-diphenylbicyclo[4.1.0]heptane ( C ) (CAS 145630-02-0), respectively. Two peaks eluting at 16.97 and 17.24 min were identified as the ortho and para products of diphenylcarbene addition to toluene in an 11:1 ratio, 1-(diphenylmethyl)-4-methyl-benzene ( D ) (CAS 603-37-2) and 1-(diphenylmethyl)-2-methyl-benzene ( E ) (CAS 17016-20-5), respectively.…”

Section: Methodsmentioning

confidence: 99%

Dehydrodechlorination of Methylene Chloride, Chloroform, and Chlorodiphenylmethane in the Presence of Ga/N Lewis Pairs

et al. 2016

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Transmetalation occurs upon addition of GaCl3 to (quinolin-8-yl)trimethylstannane. The compound dissolves immediately in pyridine, and recrystallization gives dichloropyridinyl(quinolin-8-yl)gallium(III). In chloroform, the compound bis-μ-(quinolin-8-yl)-μ-chloro-dichlorodigallium(III) tetrachlorogallate could be isolated in small quantities; however, the major product was trichloro(quinolinium-8-yl)gallate(III) zwitterion. The zwitterion also formed upon addition of methylene chloride or chlorodiphenylmethane. We hypothesize that the highly electrophilic digallyl cation abstracts chloride to form a carbocation and that proton transfer from the carbocation to the quinoline nitrogen affords transient carbenes. In particular, diphenyl carbene forms from dehydrodechlorination of chlorodiphenylmethane in toluene/cyclohexene to give a well-defined mixture of products due to cyclopropanation and C–H insertion reactions. Dichloropyridinyl(quinolin-8-yl)gallium(III) undergoes reaction with chloroform only at elevated temperature to yield quinolinium tetrachlorogallate salt as the product. This salt also forms in the reaction of chloroform with GaCl3 and quinoline at elevated temperature. The zwitterion could be converted to quinolinium tetrachlorogallate upon heating, which supports the idea that it was formed initially as an intermediate. Thus, the Ga/N Lewis pairs appear capable of dehydrodechlorination of chloroalkanes.

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Nickel-catalyzed reactions of 3,4-benzo-1,1,2,2-tetraethyl-1,2-disilacyclobut-3-ene with carbonyl compounds

Cited by 31 publications

References 0 publications

Stable bis(silyl)nickel complexes with o-carboranyl unit: a facile double silylation of alkynes and alkenes

Stable bis(silyl)nickel complexes with o-carboranyl unit: a facile double silylation of alkynes and alkenes

Nickel-Catalyzed Reactions of Benzo[1,2:4,5]bis(1,1,2,2-tetraethyl-1,2-disilacyclobut-3-ene) with Alkynes and Ketones

Dehydrodechlorination of Methylene Chloride, Chloroform, and Chlorodiphenylmethane in the Presence of Ga/N Lewis Pairs

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