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Volumn 132, Issue 2, 2010, Pages 686-693

Synthetic applications of Pd(II)-catalyzed C-H carboxylation and mechanistic insights: Expedient routes to anthranilic acids, oxazolinones, and quinazolinones

Author keywords

[No Author keywords available]

Indexed keywords

ANILIDES; ANIONIC LIGANDS; ANTHRANILIC ACID; BENZOXAZINONES; C-H BOND; CATALYZED REACTIONS; EFFICIENT STRATEGY; P-TOLUENESULFONATES; PALLADACYCLES; PTOLUENESULFONIC ACID; QUINAZOLINONES; REACTION CONDITIONS; REACTION PATHWAYS; REDUCTIVE ELIMINATION; SYNTHETIC APPLICATION;

EID: 74949120125     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9077705     Document Type: Article
Times cited : (292)

References (77)
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    • Reference 5
    • (b) Reference 5.
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    • For carboxylation with formic acid, see: d
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    • For example, Raltitrexed (Tomudex, marketed for colorectal cancer, Ispinesib (phase II for solid tumors, and Tempostatin phase II for bladder cancer
    • For example, Raltitrexed (Tomudex, marketed for colorectal cancer), Ispinesib (phase II for solid tumors), and Tempostatin (phase II for bladder cancer).
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    • Formation of dicarboxylated product was not observed. The exclusive monoselectivity is due to the lack of reactivity of the electron-deficient arenes in the carboxylated products. Furthermore, bis-chelation of Pd(II) catalyst with the acetyl and the newly generated carboxyl groups also makes it difficult for the Pd(II) to reach the remaining ortho-CH-bonds.
    • Formation of dicarboxylated product was not observed. The exclusive monoselectivity is due to the lack of reactivity of the electron-deficient arenes in the carboxylated products. Furthermore, bis-chelation of Pd(II) catalyst with the acetyl and the newly generated carboxyl groups also makes it difficult for the Pd(II) to reach the remaining ortho-CH-bonds.
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    • While our work on the synthesis of benzoxazinones and quinazolinones via the activation of ortho-C-H bonds in aniline derivatives was in progress, Lloyd-Jones, Booker-Milburn, and co-workers reported a C-H carbonylation protocol using phenylurea as the directing group: Houlden, C. E, Hutchby, M, Bailey, C. D, Ford, J. G, Tyler, S. N. G, Gagne, M. R, Lloyd-Jones, G. C, Booker-Milburn, K. I. Angew. Chem, Int. Ed. 2009, 48, 1830-1833
    • While our work on the synthesis of benzoxazinones and quinazolinones via the activation of ortho-C-H bonds in aniline derivatives was in progress, Lloyd-Jones, Booker-Milburn, and co-workers reported a C-H carbonylation protocol using phenylurea as the directing group: Houlden, C. E.; Hutchby, M.; Bailey, C. D.; Ford, J. G.; Tyler, S. N. G.; Gagne, M. R.; Lloyd-Jones, G. C.; Booker-Milburn, K. I. Angew. Chem., Int. Ed. 2009, 48, 1830-1833.
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    • For the preparation of benzoxazinone 1h, see: (a) Nagase, T.; Mizutani, T.; Ishikawa, S.; Sekino, E.; Sasaki, T.; Fujimura, T.; Ito, S.; Mitobe, Y.; Miyamoto, Y.; Yoshimoto, R.; Tanaka, T.; Ishihara, A.; Takenaga, N.; Tokita, S.; Fukami, T.; Sato, N. J. Med. Chem. 2008, 51, 4780-4789.
    • For the preparation of benzoxazinone 1h, see: (a) Nagase, T.; Mizutani, T.; Ishikawa, S.; Sekino, E.; Sasaki, T.; Fujimura, T.; Ito, S.; Mitobe, Y.; Miyamoto, Y.; Yoshimoto, R.; Tanaka, T.; Ishihara, A.; Takenaga, N.; Tokita, S.; Fukami, T.; Sato, N. J. Med. Chem. 2008, 51, 4780-4789.
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    • The mixed anhydride 1f was prepared in situ. See Experimental Section for details.
    • (b) The mixed anhydride 1f was prepared in situ. See Experimental Section for details.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.