- Two-carbon ring expansion of 1-indanones via insertion of ethylene into carbon-carbon bonds
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A rhodium-catalyzed direct insertion of ethylene into a relatively unstrained carbon-carbon bond in 1-indanones is reported, which provides a two-carbon ring expansion strategy for preparing seven-membered cyclic ketones. As many 1-indanones are commercially available and ethylene is inexpensive, this strategy simplifies synthesis of benzocycloheptenones that are valuable synthetic intermediates for bioactive compounds but challenging to prepare otherwise. In addition, the reaction is byproduct-free, redox neutral, and tolerant of a wide range of functional groups, which may have implications on unconventional strategic bond disconnections for preparing complex cyclic molecules.
- Xia, Ying,Ochi, Shusuke,Dong, Guangbin
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supporting information
p. 13038 - 13042
(2019/08/26)
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- Intermolecular addition reaction to alkenes of acylmolybdenum complexes generated by oxidative addition of aryl or alkenyl halides with molybdenum(0) carbonyl complexes
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Acylmolybdenum species, generated by oxidative addition of aryl or alkenyl halides with molybdenum(0) carbonyl complex followed by carbon monoxide insertion, added to various kinds of alkenes intermolecularly to give simple addition products in good yields without formation of carbonylative Heck-type products. Georg Thieme Verlag Stuttgart.
- Sangu, Kenichiro,Watanabe, Toru,Takaya, Jun,Iwasawa, Nobuharu
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p. 929 - 933
(2008/02/02)
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- Photochemical preparation of highly functionalized 1-indanones
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A series of o-alkylphenyl alkyl ketones 1 were synthesized by different methods. The presence of a leaving group X adjacent to the carbonyl group is the special peculiarity of these ketones. Upon irradiation the keto carbonyl group of these compounds undergoes an n-π* excitation followed by a 1,5-hydrogen migration from the o-alkyl substituent to the carbonyl oxygen atom. The thus formed 1,4-diradicals are subject to a very rapid elimination of acid HX, giving 1,5-diradicals. We called this process spin center shift. After intersystem crossing these diradicals cyclize to 1-indanones 20 in good yields. Depending on the solvent and on substituents, o-alkoxyalkyl ketones 22 or benzo-[c]furanes 21 are obtained as byproducts. The mechanism of the cyclization was elucidated by quantum chemical calculations and kinetic measurements.
- Wessig, Pablo,Glombitza, Clemens,Mueller, Gunnar,Teubner, Janek
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p. 7582 - 7591
(2007/10/03)
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- Cyclization of aryl acyl radicals generated from S-(4-cyano)phenyl thiolesters by a nickel complex catalyzed electroreduction
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Aromatic acyl radicals generated from S-(4-cyano)phenyl 2-alkenylthiobenzoate by a nickel complex catalyzed electroreduction undergo 5- and 6-exo cyclization to give 1-indanone and dihydro-1-naphthalenone derivatives, respectively.
- Ozaki, Shigeko,Adachi, Masashi,Sekiya, Sayaka,Kamikawa, Rie
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p. 4586 - 4589
(2007/10/03)
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- Synthesis of benzocyclic ketones via palladium-catalyzed cyclization of ω-(2-iodoaryl)alkanenitriles
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An efficient procedure for the synthesis of 2,2-disubstituted benzocyclic ketones by intramolecular carbopalladation of nitriles has been developed. The cyclization of substituted 3-(2-iodoaryl)propanenitriles affords indanones in high yields. The reactio
- Pletnev, Alexandre A.,Larock, Richard C.
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p. 2133 - 2136
(2007/10/03)
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- Carbopalladation of nitriles: Synthesis of benzocyclic ketones and cyclopentenones via Pd-catalyzed cyclization of ω-(2-iodoaryl)alkanenitriles and related compounds
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An efficient procedure for the synthesis of 2,2-disubstituted benzocyclic ketones by intramolecular carbopalladation of nitriles has been developed. The cyclization of substituted 3-(2-iodoaryl)-propanenitriles affords indanones in high yields. The reaction is compatible with a wide variety of functional groups. This methodology has been extended to the synthesis of tetralones and cyclopentenones.
- Pletnev, Alexandre A.,Larock, Richard C.
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p. 9428 - 9438
(2007/10/03)
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