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Volumn 49, Issue 33, 2010, Pages 5746-5749

Regiodivergent ligand-controlled rhodium-catalyzed [(2+2)+2] carbocyclization reactions with alkyl substituted methyl propiolates

Author keywords

Carbocyclization; Diastereoselective; Metallacycle; Regiodivergent reactions; Rhodium

Indexed keywords

ANCILLARY LIGANDS; CARBOCYCLIZATION; CARBOCYCLIZATION REACTIONS; DIASTEREO-SELECTIVITY; DIASTEREOSELECTIVE; METALLACYCLE; METALLACYCLES; NEUTRAL COMPLEXES; REGIOISOMERS; RHODIUM-CATALYZED; SALT METATHESIS; SELECTIVE FORMATION; SILVER SALTS;

EID: 77955322926     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201002117     Document Type: Article
Times cited : (41)

References (35)
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    • For excellent reviews on metal-catalyzed [2+2+2] carbocyclizations involving 1,6-enynes, see
    • For excellent reviews on metal-catalyzed [2+2+2] carbocyclizations involving 1,6-enynes, see:
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    • For examples of metal-catalyzed and metal-mediated intermolecular [(2+2)+2] carbocyclizations of tethered 1,6-enynes with alkynes see: a
    • For examples of metal-catalyzed and metal-mediated intermolecular [(2+2)+2] carbocyclizations of tethered 1,6-enynes with alkynes see: a) Co: C.-A. Chang, J. A. King, Jr., K. P. C Vollhardt, J. Chem. Soc. Chem. Commun. 1981, 53
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    • [4b]
    • [4b]
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    • For a recent example of ligand-controlled carbocyclization reactions, see
    • For a recent example of ligand-controlled carbocyclization reactions, see: P. Mauleón, R. M. Zeldin, A. Z. González, F. D. Toste, J. Am. Chem. Soc. 2009, 131, 6348.
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    • The term regiodivergent, adapted from. Nógrádi's definition of stereoconvergence, refers to the formation of two isomeric products from the same starting material(s). VCH, New York
    • The term regiodivergent, adapted from. Nógrádi's definition of stereoconvergence, refers to the formation of two isomeric products from the same starting material(s). M. Nógrádi in Stereoselective Synthesis, VCH, New York, 1996.
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    • [3d] (Figure Presented)
    • [3d] (Figure Presented)
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    • For other transition metal-catalyzed reactions that have implicated the silver salt for poor selectivity, see: a
    • For other transition metal-catalyzed reactions that have implicated the silver salt for poor selectivity, see: a) F. Miyazaki, K. Uotsu, M. Shibasaki, Tetrahedron 1998, 54, 13073
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    • [4b] For example, treatment of enyne 1b with methyl phenyl propiolate 2e (R = Ph) under the optimal conditions, furnished the bicyclohexa-1,3-diene 4m in 52% yield and with ≥ 19:1 regioselectivity
    • [4b] For example, treatment of enyne 1b with methyl phenyl propiolate 2e (R = Ph) under the optimal conditions, furnished the bicyclohexa-1,3-diene 4m in 52% yield and with ≥ 19:1 regioselectivity.
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    • [4b,6]
    • [4b,6]
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    • The analogous carbocyclization reaction (Table 1, entry 1) in tetrahydrofuran furnished the bicyclohexa-1,3-diene 4a in 76% yield as the major regioisomer (r.s. = 4:1), which indicates the solvent is not playing a major role on the reversal of the regioselection
    • The analogous carbocyclization reaction (Table 1, entry 1) in tetrahydrofuran furnished the bicyclohexa-1,3-diene 4a in 76% yield as the major regioisomer (r.s. = 4:1), which indicates the solvent is not playing a major role on the reversal of the regioselection.
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    • For examples of selective formation of metallacyclopentenes in the presence of both alkynes and alkenes, see: M. Jeganmohan, C.-H. Cheng, Chem. Eur. J. 2008, 14, 10876.
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    • For selected examples of metal-vinyl versus metal-alkyl migratory insertion, see: a
    • For selected examples of metal-vinyl versus metal-alkyl migratory insertion, see: a) Y. Wakatsuki, K. Aoki, H. Yamazaki, J. Am. Chem. Soc. 1979, 101, 1123
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    • For a recent example of the regioselective insertion of polarized alkynes to form metallacycles in which the electron-withdrawing group is adjacent to the metal, see
    • For a recent example of the regioselective insertion of polarized alkynes to form metallacycles in which the electron-withdrawing group is adjacent to the metal, see: M. Paneque, C. M. Posadas, M. L. Poveda, N. Rendón, E. Álvarez, K. Mereiter, Chem. Eur. J. 2007, 13, 5160.
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    • For the rationalization of the geometry of metallacycles analogous to b and e, see: a
    • For the rationalization of the geometry of metallacycles analogous to b and e, see: a) cycle A: C. E. Dean, R. D. W. Kemmitt, D. R. Russell, M. D. Schilling, J. Organomet. Chem. 1980, 187, C1
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.