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Volumn 69, Issue 10, 2004, Pages 3478-3487

Addition of Bifunctional Organoboron Reagents to Strained Alkenes. Carbon-Carbon Bond Formation with Rh(I) Catalysis in Aqueous Media

Author keywords

[No Author keywords available]

Indexed keywords

ADDITION REACTIONS; BORON COMPOUNDS; CATALYSIS; COMPLEXATION; RHODIUM COMPOUNDS; SOLUTIONS; STEREOCHEMISTRY; STRAIN;

EID: 2442502437     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo049874k     Document Type: Article
Times cited : (70)

References (84)
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    • Cornils, B., Herrmann, W. A., Eds.; Wiley-VCH: Weinheim, Germany
    • For a review on organometallic chemistry in water, see: Herrmann, W. A. In Aqueous-Phase Organometallic Chemistry; Cornils, B., Herrmann, W. A., Eds.; Wiley-VCH: Weinheim, Germany, 1998; pp 35-45.
    • (1998) Aqueous-Phase Organometallic Chemistry , pp. 35-45
    • Herrmann, W.A.1
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    • Reviews on Rh-catalyzed couplings: (a) Fagnou, K.; Lautens, M. Chem. Rev. 2003, 103, 169.
    • (2003) Chem. Rev. , vol.103 , pp. 169
    • Fagnou, K.1    Lautens, M.2
  • 20
    • 0242467700 scopus 로고    scopus 로고
    • Some recent applications of rhodium catalysis for the formation of C-C bonds: (a) Dhanalakshmi, K.; Vaultier; M. Tetrahedron 2003, 59, 9907.
    • (2003) Tetrahedron , vol.59 , pp. 9907
    • Dhanalakshmi, K.1    Vaultier, M.2
  • 44
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    • Our previous study demonstrated that halide substituents on the boronic acid coupling partner survive the cross-coupling conditions; see ref 15 and for other examples indicating the resistance of Rh insertion into aryl halide bonds at low temperature; see: (a) Ishiyama, T.; Hartwig, J. J. Am. Chem. Soc. 2000, 122, 12043.
    • (2000) J. Am. Chem. Soc. , vol.122 , pp. 12043
    • Ishiyama, T.1    Hartwig, J.2
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    • note
    • This ligand is commercially available from Strem Chemicals.
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  • 50
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    • (a) Trost, B. M. Science 1991, 254, 1471.
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    • 2442582193 scopus 로고    scopus 로고
    • note
    • f to the product on silica gel, the loading is reduced to 1.05-1.1 equiv. In all cases, this reduction has no detrimental effect on selectivity or yield of the reaction.
  • 75
    • 2442418711 scopus 로고    scopus 로고
    • note
    • A control reaction was undertaken to determine the relative propensity of a strained alkene and a Michael acceptor toward carborhodation in the present system. When 1.5 equiv each of norbornene and ethyl acrylate were mixed with 1 equiv of phenylboronic acid under standard reaction conditions, only ethyl cinnamate was obtained, indicating that the arylrhodium species generated in this reaction is highly nucleophilic in character. Increasing the amount of norbornene to 5 equiv did not change the outcome of the reaction.
  • 76
    • 2442537893 scopus 로고    scopus 로고
    • note
    • 3P (170°). Although t-Bu-amphos chloride has not been measured, its cone angle is assumed to be similar to that of t-BuaP (185°). See ref 24b.
  • 77
    • 2442489682 scopus 로고    scopus 로고
    • note
    • The more reactive [2.2.1]oxabicyclic alkenes were also tested, as well as norbornene, and did not yield any desired ring-closed products.
  • 78
    • 2442601152 scopus 로고    scopus 로고
    • note
    • The C-H insertion product as well as the minor cyclized product was only observed when fluoride was used as base at high temperatures. Fluoride may promote the oxidative process required for C-H insertion, by stabilizing the Rh(III) state.
  • 79
    • 2442571801 scopus 로고    scopus 로고
    • note
    • Presumably, installation of a functional group at the 4-position, such as a methyl group, would prevent this C-H insertion process and promote formation of the desired cyclized product. This process is under examination.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.