16783-22-5Relevant articles and documents
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Negishi,E.,Brown,H.C.
, p. 77 - 89 (1974)
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Berson,J.A.,Jones,M.
, p. 5019 - 5020 (1964)
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House,H.O.,Blankley,C.J.
, p. 1741 - 1748 (1967)
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Borch,Fields
, p. 1480 (1969)
Highly Selective Hydrogenation of Aromatic Ketones and Phenols Enabled by Cyclic (Amino)(alkyl)carbene Rhodium Complexes
Wei, Yu,Rao, Bin,Cong, Xuefeng,Zeng, Xiaoming
supporting information, p. 9250 - 9253 (2015/08/11)
Air-stable Rh complexes ligated by strongly σ-donating cyclic (amino)(alkyl)carbenes (CAACs) show unique catalytic activity for the selective hydrogenation of aromatic ketones and phenols by reducing the aryl groups. The use of CAAC ligands is essential for achieving high selectivity and conversion. This method is characterized by its good compatibility with unsaturated ketones, esters, carboxylic acids, amides, and amino acids and is scalable without detriment to its efficiency.
Acyl Radicals: Intermolecular and Intramolecular Alkene Addition Reactions
Boger, Dale L.,Mathvink, Robert J.
, p. 1429 - 1443 (2007/10/02)
A full study of the use of phenyl selenoesters as precursors to acyl radicals and their subsequent participation in intermolecular and intramolecular alkene addition reactions is detailed.Primary alkyl-, vinyl-, and arylsubstituted acyl radicals generated by Bu3SnH treatment of the corresponding phenyl selenoesters participate cleanly in intermolecular addition reactions with alkenes bearing electron-withdrawing or radical-stabilizing substituents at rates that exceed those of the potentially competitive decarbonylation or reduction.Similarly, their intramolecular addition to activated or unactivated alkenes proceeds without significant competitive reduction or decarbonylation and at rates generally >/= 1 x 106 s-1 with some occuring at rates >/= 3 x 107 s-1.Consistent with their behavior in intermolecular addition reactions, the 5-exo-trig cyclizations of secondary and tertiary alkyl-substituted acyl radicals to an unactivated olefin acceptor may be accompanied by varying degrees of decarbonylation, even under low-temperature free-radical conditions.Studies are presented which suggest that the intramolecular additions of acyl radicals to alkenes under the conditions detailed herein may be regarded as irreversible, kinetically controlled processes which exhibit regioselectivity that is predictable based on well-established empirical rules set forth for the analogous free-radical cyclization reactions of alkyl radicals.
Trimethylsilyl Cyanide - A Reagent for Umpolung, XII. Intramolecular Diels-Alder Reaction of Dienals via Umpolung
Fischer, Klaus,Huenig, Siegfried
, p. 2590 - 2608 (2007/10/02)
Umpolung of dienals 1 and 2 with trimethylsilyl- or triethylsilyl cyanide and reaction with olefinic alkylating reagents 7-10 furnishes products 11-16 in high yields.On heating to 180 deg C these products, containing a diene and a dienophilic moiety, undergo in most cases quantitative intramolecular Diels-Alder reactions.Since the cycloadducts can be deprotected under very mild conditions, hexahydro-indenones (22, 25) and -naphthalinones (27, 29) can be synthesized for the first time avoiding isomerisation of the double bond.Intramolecular cycloadditions without protected carbonyl groups in the precursor (19, 21) yield hexahydronaphthalinones (30, 34) with conjugated double bonds exclusively, whereas ring closure to hexahydro-indenones (33) fails.Related examples described in the literature suffer from the same drawback.
