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Volumn 128, Issue 39, 2006, Pages 12954-12962

Hydrogen-bond-directed highly stereoselective synthesis of Z-enamides via Pd-catalyzed oxidative amidation of conjugated olefins

Author keywords

[No Author keywords available]

Indexed keywords

PD CATALYZED OXIDATIVE AMIDATION; PHOSPHINE OXIDES; STEREOSELECTIVE SYNTHESIS; Z ENAMIDES;

EID: 33749531743     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0639315     Document Type: Article
Times cited : (143)

References (142)
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    • For an example of the oxidation of β-amido esters to Z-enamides using Dess-Martin periodinate, see: Nicolaou, K. C.; Mathison, C. J. N. Angew. Chem., Int. Ed. 2005, 44, 5992-5997.
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    • Kish et al. also reported that the cis/trans isomerization was induced under photochemical conditions in a solvent-dependent manner and approximated that a 6.5:1 ratio of the trans- and cis-isomers was obtained in DMF. Suh, E. M.; Kishi, Y. J. Am. Chem. Soc. 1994, 116, 11205-11206.
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    • Porco et al. demonstrated that copper-catalyzed coupling of primary amides with E-vinyl iodides bearing a β-amide group afforded Z-enamides albeit in rather low yields (18-25%). It was reasoned that the stereocontrol was related to the higher acidity of the N-H in conjugated amides, thus leading to the formation of an intramolecular H-bond. Han, C.; Shen, R.; Su, S.; Porco, J. A., Jr. Org. Lett. 2004, 6, 27-30.
    • (2004) Org. Lett. , vol.6 , pp. 27-30
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    • For selected examples of related works from this laboratory, see: (a) Chang, S.; Yang, S. H.; Lee, P. H. Tetrahedron Lett. 2001, 42, 4833-4835.
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    • For general accounts of the Wacker reaction, see: (a) Tsuji, J. Synthesis 1984, 369-384.
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  • 107
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    • note
    • The side product was determined to be ethyl 3-oxo-Δ1α- isoisoindolineacetate.
  • 111
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    • note
    • The chemical shift of the N-H proton is not dependent upon the concentration of isolated Z-enamide sample. Therefore, the possibility of a contribution from an intermolecular H-bond seems to be quite low.
  • 112
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    • note
    • When ethyl cis-crotonate and ethyl trans-cinnamate were applied, the corresponding enamides were not produced, which suggests that the vinyl substituents at the β position with respect to the carbonyl group of conjugated olefins might significantly inhibit the progress of the reaction.
  • 118
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    • note
    • Photoirradiation of Z-3 in chloroform at 300 nm gave Z/E = 1:1 within 10 min. However, after reaching Z/E = ca. 3 in 1 h, both compounds decomposed under longer irradiation. Photoirradiation of Z-3 in chloroform at 250 nm resulted in decomposition of the starting material within 10 min. The time course of photoirradiation at 350 nm was monitored every 1 h.
  • 126
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    • note
    • It can be also considered that the amidopalladation proceeds through zwitterionic intermediates which are deprotonated by chloride anion to afford anionic palladium species in analogy to Stahl's aerobic oxidative amination reactions, as demonstrated in ref 27.
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    • note
    • B3LYP/6-31G(d) is used for calculation of the energy level of final products only.
  • 136
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    • note
    • a for E is 0.29 kcal/mol.
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    • note
    • For examples of β-hydride elimination as a rate-determining step by the similar approach, see ref 45g.
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    • note
    • For the Cu-mediated N-vinylation of amides with (E)-allyl-β- iodoacrylate for the synthesis of CJ-15,801 and its analogues, see ref 23.
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    • note
    • For the deallylation procedure from the same precursor to give free cis-15,801, see ref 21.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.