메뉴 건너뛰기




Volumn 21, Issue 38, 2015, Pages 13225-13228

Ni-Catalyzed Synthesis of Fluoroarenes via [2+2+2] Cycloaddition Involving α-Fluorine Elimination

Author keywords

alkynes; C F bond activation; fluoroalkenes; fluoroarenes; nickel

Indexed keywords

CATALYSIS; FLUORINE COMPOUNDS; HYDROCARBONS; MOLECULES; REDUCTION;

EID: 84940889539     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.201502744     Document Type: Article
Times cited : (23)

References (70)
  • 8
    • 0001590919 scopus 로고
    • A. Roe, Org. React. 1949, 5, 193-228;
    • (1949) Org. React. , vol.5 , pp. 193-228
    • Roe, A.1
  • 14
    • 77955214138 scopus 로고    scopus 로고
    • Angew. Chem. 2010, 122, 2261-2264;
    • (2010) Angew. Chem. , vol.122 , pp. 2261-2264
  • 16
    • 77951146731 scopus 로고    scopus 로고
    • Angew. Chem. 2010, 122, 2265-2268.
    • (2010) Angew. Chem. , vol.122 , pp. 2265-2268
  • 22
    • 84901486528 scopus 로고    scopus 로고
    • Angew. Chem. 2013, 125, 8791-8794.
    • (2013) Angew. Chem. , vol.125 , pp. 8791-8794
  • 28
    • 84921508225 scopus 로고    scopus 로고
    • Angew. Chem. 2014, 126, 7694-7698.
    • (2014) Angew. Chem. , vol.126 , pp. 7694-7698
  • 41
    • 84940895473 scopus 로고    scopus 로고
    • For Ni-catalyzed [2+2+2] reactions between one molecule of alkenes and two molecules of alkynes, see
    • For Ni-catalyzed [2+2+2] reactions between one molecule of alkenes and two molecules of alkynes, see:
  • 46
    • 77149153815 scopus 로고    scopus 로고
    • Angew. Chem. 2009, 121, 5839-5842;
    • (2009) Angew. Chem. , vol.121 , pp. 5839-5842
  • 53
    • 72149086380 scopus 로고    scopus 로고
    • For a review on transition-metal-mediated α-fluorine elimination, see
    • For a review on transition-metal-mediated α-fluorine elimination, see:, R. P. Hughes, Eur. J. Inorg. Chem. 2009, 4591-4606.
    • (2009) Eur. J. Inorg. Chem. , pp. 4591-4606
    • Hughes, R.P.1
  • 55
    • 84904509963 scopus 로고    scopus 로고
    • Angew. Chem. 2010, 122, 8899-8902.
    • (2010) Angew. Chem. , vol.122 , pp. 8899-8902
  • 56
    • 77249109340 scopus 로고    scopus 로고
    • Structures of major and minor regioisomers were characterized by 2D NMR measurements. Minor products were thus found to be m-terphenyl derivatives. For details, see the Supporting Information. For regioselectivity on nickel-catalyzed coupling reactions of alkynes via oxidative cyclization, see
    • Structures of major and minor regioisomers were characterized by 2D NMR measurements. Minor products were thus found to be m-terphenyl derivatives. For details, see the Supporting Information. For regioselectivity on nickel-catalyzed coupling reactions of alkynes via oxidative cyclization, see:, P. Liu, P. McCarren, P. H.-Y. Cheong, T. F. Jamison, K. N. Houk, J. Am. Chem. Soc. 2010, 132, 2050-2057.
    • (2010) J. Am. Chem. Soc. , vol.132 , pp. 2050-2057
    • Liu, P.1    McCarren, P.2    Cheong, P.H.-Y.3    Jamison, T.F.4    Houk, K.N.5
  • 57
    • 84940896706 scopus 로고    scopus 로고
    • Reactions with terminal alkynes such as 1-hexyne, phenylacetylene, and trimethylsilylacetylene afforded the corresponding fluoroarenes, albeit in 5%, 3%, and 5% yields (determined by 19F NMR spectroscopy with PhCF3 as an internal standard), respectively
    • Reactions with terminal alkynes such as 1-hexyne, phenylacetylene, and trimethylsilylacetylene afforded the corresponding fluoroarenes, albeit in 5%, 3%, and 5% yields (determined by 19F NMR spectroscopy with PhCF3 as an internal standard), respectively.
  • 58
    • 84940895816 scopus 로고    scopus 로고
    • A stepwise oxidative cyclization model satisfactorily illustrates the experimental results. This stepwise model consists of (i) rapid pre-equilibrium between the reactants (Ni0 and 1) and the intermediary nickelacyclopropane (see ref. [9]) and (ii) subsequent slow insertion of 2 into the nickelacyclopropane. For details, see the Supporting Information
    • A stepwise oxidative cyclization model satisfactorily illustrates the experimental results. This stepwise model consists of (i) rapid pre-equilibrium between the reactants (Ni0 and 1) and the intermediary nickelacyclopropane (see ref. [9]) and (ii) subsequent slow insertion of 2 into the nickelacyclopropane. For details, see the Supporting Information.
  • 59
    • 84940891832 scopus 로고    scopus 로고
    • The proposed oxidative cyclization is supported by Hoberg's and Chatani's reports. See
    • The proposed oxidative cyclization is supported by Hoberg's and Chatani's reports. See:
  • 61
    • 78449297482 scopus 로고    scopus 로고
    • Ref. [15]. See also
    • Ref. [15]. See also, M. Takachi, N. Chatani, Org. Lett. 2010, 12, 5132-5134.
    • (2010) Org. Lett. , vol.12 , pp. 5132-5134
    • Takachi, M.1    Chatani, N.2
  • 62
    • 84940899612 scopus 로고    scopus 로고
    • In the case of the reaction of 1,1-difluoro-1,6-enyne 5 with diphenylacetylene (2a), β-hydrogen elimination yielding the corresponding fluoroarene 6 was sluggish, probably due to the rigid bicyclic system of the intermediate. Thus, in the presence of the reductant, Et3B-iPrOLi, transmetalation from the intermediary cyclohexadienylnickel(II) fluoride corresponding to C in Scheme 2 preferably occurred rather than β-hydrogen elimination, leading to the cyclohexadiene. To avoid confusion, we herein demonstrate that the stoichiometric reaction, conducted in the absence of the reductant, selectively afforded the corresponding fluoroarene 6 [Eq. (1)]
    • In the case of the reaction of 1,1-difluoro-1,6-enyne 5 with diphenylacetylene (2a), β-hydrogen elimination yielding the corresponding fluoroarene 6 was sluggish, probably due to the rigid bicyclic system of the intermediate. Thus, in the presence of the reductant, Et3B-iPrOLi, transmetalation from the intermediary cyclohexadienylnickel(II) fluoride corresponding to C in Scheme 2 preferably occurred rather than β-hydrogen elimination, leading to the cyclohexadiene. To avoid confusion, we herein demonstrate that the stoichiometric reaction, conducted in the absence of the reductant, selectively afforded the corresponding fluoroarene 6 [Eq. (1)].
  • 63
    • 84940888653 scopus 로고    scopus 로고
    • Since generation of ethylene and dihydrogen during the reaction was confirmed by each gas detector, a β-hydrogen elimination-reductive elimination sequence definitely occurred as a route from NiII to Ni0
    • Since generation of ethylene and dihydrogen during the reaction was confirmed by each gas detector, a β-hydrogen elimination-reductive elimination sequence definitely occurred as a route from NiII to Ni0.
  • 64
    • 84940895709 scopus 로고    scopus 로고
    • For a review on oxidative C--H/C-H coupling, see
    • For a review on oxidative C--H/C-H coupling, see:
  • 67
    • 84891015960 scopus 로고    scopus 로고
    • Angew. Chem. 2013, 125, 10084-10115.
    • (2013) Angew. Chem. , vol.125 , pp. 10084-10115
  • 70
    • 33751160357 scopus 로고    scopus 로고
    • For a modular synthesis of substituted fluoroarenes, see
    • For a modular synthesis of substituted fluoroarenes, see:, Y. Wang, D. J. Burton, Tetrahedron Lett. 2006, 47, 9279-9281.
    • (2006) Tetrahedron Lett. , vol.47 , pp. 9279-9281
    • Wang, Y.1    Burton, D.J.2


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.