Search citation statements
Paper Sections
Citation Types
Year Published
Publication Types
Relationship
Authors
Journals
Secondary phosphine oxides (SPOs) have been widely used for the synthesis of tertiary phosphine oxides and have found applications as Wittig-Horner reagents [1][2] and, later, as effective ligands for transition-metal complexes.[3] Recently, Li et al. showed that SPOs form air-stable palladium complexes, such as POPd1, when they are mixed with PdCl 2 (MeCN) 2 and then treated with Et 3 N.[4] These complexes proved efficient as catalysts in several cross-coupling reactions [4][5] as well as in asymmetric allylic alkylations.[6] Recent reports showed also that these new ligands are suitable for other types of catalyzed reactions such as the hydrolysis of nitriles [7] and the asymmetric hydrogenation of imines [8] and alkenes.[9] Our continued interest in the metal-catalyzed cycloaddition reactions between alkynes and norbornadiene [10] prompted us to investigate the catalytic behavior of palladium(ii) complexes coordinated by SPOs.First, we developed an easier way to synthesize the palladium catalyst 1. Upon treatment of Pd(OAc) 2 with tertbutyl(phenyl)phosphane oxide (L 1), dihydrogen di-macetatotetrakis(tert-butylphenylphosphinito -k -P)dipalladate (1) was quantitatively obtained without further treatment (Scheme 1).[11] Second, as a model we examined the reaction of phenylethyne (3 a) with norbornadiene (2) in the presence of 2.5 mol % of 1 in toluene at 50 8C for 24 h. Unexpectedly, the palladium(ii) complex 1 coordinated by L 1 favored the formation of benzylidenecyclopropane (4 a) as a single diastereomer in 17 % yield (Scheme 2) and contaminated by an unidentified byproduct (5 %). Surprisingly, a similar reaction using the known chloro-bridged analogue 5[6a-12] as catalyst did not work. Furthermore, in the reaction catalyzed by 5, the addition of 10 mol % of AgOAc (4 equiv relative to
Secondary phosphine oxides (SPOs) have been widely used for the synthesis of tertiary phosphine oxides and have found applications as Wittig-Horner reagents [1][2] and, later, as effective ligands for transition-metal complexes.[3] Recently, Li et al. showed that SPOs form air-stable palladium complexes, such as POPd1, when they are mixed with PdCl 2 (MeCN) 2 and then treated with Et 3 N.[4] These complexes proved efficient as catalysts in several cross-coupling reactions [4][5] as well as in asymmetric allylic alkylations.[6] Recent reports showed also that these new ligands are suitable for other types of catalyzed reactions such as the hydrolysis of nitriles [7] and the asymmetric hydrogenation of imines [8] and alkenes.[9] Our continued interest in the metal-catalyzed cycloaddition reactions between alkynes and norbornadiene [10] prompted us to investigate the catalytic behavior of palladium(ii) complexes coordinated by SPOs.First, we developed an easier way to synthesize the palladium catalyst 1. Upon treatment of Pd(OAc) 2 with tertbutyl(phenyl)phosphane oxide (L 1), dihydrogen di-macetatotetrakis(tert-butylphenylphosphinito -k -P)dipalladate (1) was quantitatively obtained without further treatment (Scheme 1).[11] Second, as a model we examined the reaction of phenylethyne (3 a) with norbornadiene (2) in the presence of 2.5 mol % of 1 in toluene at 50 8C for 24 h. Unexpectedly, the palladium(ii) complex 1 coordinated by L 1 favored the formation of benzylidenecyclopropane (4 a) as a single diastereomer in 17 % yield (Scheme 2) and contaminated by an unidentified byproduct (5 %). Surprisingly, a similar reaction using the known chloro-bridged analogue 5[6a-12] as catalyst did not work. Furthermore, in the reaction catalyzed by 5, the addition of 10 mol % of AgOAc (4 equiv relative to
Secondary phosphine oxides (SPOs) have been widely used for the synthesis of tertiary phosphine oxides and have found applications as Wittig-Horner reagents [1][2] and, later, as effective ligands for transition-metal complexes.[3] Recently, Li et al. showed that SPOs form air-stable palladium complexes, such as POPd1, when they are mixed with PdCl 2 (MeCN) 2 and then treated with Et 3 N.[4] These complexes proved efficient as catalysts in several cross-coupling reactions [4][5] as well as in asymmetric allylic alkylations.[6] Recent reports showed also that these new ligands are suitable for other types of catalyzed reactions such as the hydrolysis of nitriles [7] and the asymmetric hydrogenation of imines [8] and alkenes.[9] Our continued interest in the metal-catalyzed cycloaddition reactions between alkynes and norbornadiene [10] prompted us to investigate the catalytic behavior of palladium(ii) complexes coordinated by SPOs.First, we developed an easier way to synthesize the palladium catalyst 1. Upon treatment of Pd(OAc) 2 with tertbutyl(phenyl)phosphane oxide (L 1), dihydrogen di-macetatotetrakis(tert-butylphenylphosphinito -k -P)dipalladate (1) was quantitatively obtained without further treatment (Scheme 1).[11] Second, as a model we examined the reaction of phenylethyne (3 a) with norbornadiene (2) in the presence of 2.5 mol % of 1 in toluene at 50 8C for 24 h. Unexpectedly, the palladium(ii) complex 1 coordinated by L 1 favored the formation of benzylidenecyclopropane (4 a) as a single diastereomer in 17 % yield (Scheme 2) and contaminated by an unidentified byproduct (5 %). Surprisingly, a similar reaction using the known chloro-bridged analogue 5[6a-12] as catalyst did not work. Furthermore, in the reaction catalyzed by 5, the addition of 10 mol % of AgOAc (4 equiv relative to
We report a highly robust, general and stereoselective method for the synthesis of 3-(chloromethylene)oxindoles from alkyne-tethered carbamoyl chlorides using PdCl(PhCN) as the catalyst. The transformation involves a stereo- and regioselective chloropalladation of an internal alkyne to generate a nucleophilic vinyl Pd species, which then undergoes an intramolecular cross-coupling with a carbamoyl chloride. The reaction proceeds under mild conditions, is insensitive to the presence of moisture and air, and is readily scalable. The products obtained from this reaction are formed with >95:5 Z:E selectivity in nearly all cases and can be used to access biologically relevant oxindole cores. Through combined experimental and computational studies, we provide insight into stereo- and regioselectivity of the chloropalladation step, as well as the mechanism for the C-C bond forming process. Calculations provide support for a mechanism involving oxidative addition into the carbamoyl chloride bond to generate a high valent Pd species, which then undergoes facile C-C reductive elimination to form the final product. Overall, the transformation constitutes a formal Pd-catalyzed intramolecular alkyne chlorocarbamoylation reaction.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.