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Volumn 48, Issue 34, 2009, Pages 6262-6265

Cryptocatalytic 1,2-alkene migration in a σ-alkyl palladium diene complex

Author keywords

Alkene migration; Homogeneous catalysis; Hydrides; Isotopic labeling; Palladium

Indexed keywords

ALKENE MIGRATION; HOMOGENEOUS CATALYSIS; ISOTOPIC LABELING; PALLADIUM HYDRIDE; TRIFLATES; TRIFLUOROMETHANE SULFONIC ACID;

EID: 70349916472     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200901468     Document Type: Article
Times cited : (22)

References (45)
  • 5
    • 34548774476 scopus 로고    scopus 로고
    • For elegant labeling studies of this system, see: d
    • For elegant labeling studies of this system, see: d) B. M. M. Wheatley, B. A. Keay, J. Org. Chem. 2007, 72, 7253-7259.
    • (2007) J. Org. Chem , vol.72 , pp. 7253-7259
    • Wheatley, B.M.M.1    Keay, B.A.2
  • 23
    • 70349967601 scopus 로고    scopus 로고
    • The temporal fractional conversion should in fact be concentration independent. There is also an induction period evident with 1 (R - butenyl), see Figure 4 in reference [4a].
    • The temporal fractional conversion should in fact be concentration independent. There is also an induction period evident with 1 (R - butenyl), see Figure 4 in reference [4a].
  • 25
    • 70349969428 scopus 로고    scopus 로고
    • 6, OTs, or OAc failed. Ts-4-toluenesulfonyl.
    • 6, OTs, or OAc failed. Ts-4-toluenesulfonyl.
  • 27
    • 70349973349 scopus 로고    scopus 로고
    • -1) arises from interactions between the terminal methyl group and the approaching allyl group in 6, see the Supporting Information.
    • -1) arises from interactions between the terminal methyl group and the approaching allyl group in 6, see the Supporting Information.
  • 28
    • 70349975605 scopus 로고    scopus 로고
    • 2O) and 720420 (4) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data-request/cif.
    • 2O) and 720420 (4) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data-request/cif.
  • 29
    • 70349957906 scopus 로고    scopus 로고
    • 2O were the most efficient but varied substantially from batch to batch, even though the addition of NaF or TBAF to reactions conducted in the presence of TfOH had no effect. TBAF = tetra-n-butylammonium fluoride.
    • 2O were the most efficient but varied substantially from batch to batch, even though the addition of NaF or TBAF to reactions conducted in the presence of TfOH had no effect. TBAF = tetra-n-butylammonium fluoride.
  • 32
    • 70349956374 scopus 로고    scopus 로고
    • Preliminary DFT studies of intramolecular mechanisms identified feasible intermediates for B and C (12 and 13 kcalmol-1 above 4, but the calculated barriers in excess of 40 kcalmol-1 for C, D, and E would not be energetically accessible under the general reaction conditions 21°C, and no suitable transition state was located for pathway B. See the Supporting Information for a discussion
    • -1 for C, D, and E would not be energetically accessible under the general reaction conditions (21°C), and no suitable transition state was located for pathway B. See the Supporting Information for a discussion.
  • 35
    • 70349956390 scopus 로고    scopus 로고
    • See the Supporting Information for additional reactions of 4, and analogues, that reinforce this conclusion
    • See the Supporting Information for additional reactions of 4, and analogues, that reinforce this conclusion.
  • 36
    • 70349961393 scopus 로고    scopus 로고
    • Complexes tested: Z = diethyl, ethyl methyl, and di(tert-butyl) malonate, N-tosylamide, 4′,4′-dimethyl-3′,5′- dioxan-2′,6′-dionyl, and 3′,5′-dioxan-4-onyl. See the Supporting Information.
    • Complexes tested: Z = diethyl, ethyl methyl, and di(tert-butyl) malonate, N-tosylamide, 4′,4′-dimethyl-3′,5′- dioxan-2′,6′-dionyl, and 3′,5′-dioxan-4-onyl. See the Supporting Information.
  • 37
    • 0035477778 scopus 로고    scopus 로고
    • 2H transfers are reminiscent of a palladium-catalyzed diene cycloisomerization mediated by a Pd(H) species that has been generated in situ. Such reactions commonly display induction periods and pseudo zero-order substrate dependency: a) K. L. Bray, I. J. S. Fairlamb, J. P. H. Charmant, G. C. Lloyd-Jones, Chem. Eur. J. 2001, 7, 4205-4215;
    • 2H transfers are reminiscent of a palladium-catalyzed diene cycloisomerization mediated by a Pd(H) species that has been generated in situ. Such reactions commonly display induction periods and pseudo zero-order substrate dependency: a) K. L. Bray, I. J. S. Fairlamb, J. P. H. Charmant, G. C. Lloyd-Jones, Chem. Eur. J. 2001, 7, 4205-4215;
  • 43
    • 6044274630 scopus 로고    scopus 로고
    • 3SiH resulted in no significant change over 12 h.
    • 3SiH resulted in no significant change over 12 h.
  • 44
    • 70349941067 scopus 로고    scopus 로고
    • TfOH may also generate the active catalyst 10 from 4, for example by demethylative lactonization (see reference [12]) then β-hydride elimination at C6. Despite careful GCMS/NMR analysis, we were unable to identify any coproducts from this process.
    • TfOH may also generate the active catalyst 10 from 4, for example by demethylative lactonization (see reference [12]) then β-hydride elimination at C6. Despite careful GCMS/NMR analysis, we were unable to identify any coproducts from this process.
  • 45
    • 70349948745 scopus 로고    scopus 로고
    • 1H scrambling between C8 and C9.
    • 1H scrambling between C8 and C9.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.