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Volumn 12, Issue 9, 2006, Pages 2520-2531

Mechanism and exo-regioselectivity of organolanthanide-mediated intramolecular hydroamination/cyclization of 1,3-disubstituted aminoallenes: A computational study

Author keywords

Density functional calculations; Homogeneous catalysis; Hydroamination; Lanthanides; Reaction mechanisms

Indexed keywords

CATALYST ACTIVITY; DISSOCIATION; PROBABILITY DENSITY FUNCTION; RARE EARTH ELEMENTS; REACTION KINETICS; THERMODYNAMICS;

EID: 33644931605     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200501017     Document Type: Article
Times cited : (48)

References (107)
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    • (Eds.: G. Wilkinson, F. G. A. Stone, E. W. Abel), Pergamon Press, Oxford, Chapter 2
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    • (Ed.: S. Kobayashi), Springer, Berlin
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    • (1999) Topics in Organometallic Chemistry
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    • 33644902573 scopus 로고    scopus 로고
    • note
    • -1 (see also ref. [9c]).
  • 65
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    • b) for a computational mechanistic study of the organolanthanide-mediated intermolecular hydroamination of 1,3-dienes and primary amines, see: S. Tobisch, Chem. Eur. J. 2005, 11, 6372.
    • (2005) Chem. Eur. J. , vol.11 , pp. 6372
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    • note
    • 3+ ion size and skeletal substrate substitutions, however, have been reported to have a significant influence on the turnover-limiting barrier (see refs. [9c,21b]) which can likely be supposed for other steps as well. Accordingly, the computationally predicted energy profiles for the IHC of 4,5-heptadien-1-ylamine and (4E,6)-heptadien-1-amine cannot be compared directly in a strict sense. Turnover frequencies of the same magnitude have been measured for the IHC of 1,3-disubstituted aminoallene catalyzed by Lu- and La-based systems, such that a semiquantitative comparison of the energetics for the two substrates seems to be suitable.
  • 88
    • 0346994917 scopus 로고    scopus 로고
    • b) For metal and ancillary ligand effects on aminodiene cyclohydroamination reactions, see: S. Hong, A. M. Kawaoka, T. J. Marks, J. Am. Chem. Soc. 2003, 125, 15878.
    • (2003) J. Am. Chem. Soc. , vol.125 , pp. 15878
    • Hong, S.1    Kawaoka, A.M.2    Marks, T.J.3
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    • 33644907421 scopus 로고    scopus 로고
    • note
    • Examination by a linear-transit approach gave no indication that this process is associated with a significant enthalpic barrier.
  • 91
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    • For NMR evidence of rapid amido/amine permutation and association/dissociation of amine substrates, see ref. [5c]
    • For NMR evidence of rapid amido/amine permutation and association/dissociation of amine substrates, see ref. [5c].
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    • note
    • The located adduct species 3″-S is characterized by only a weak amidoallene - Ln chelating interaction (cf. Figure S3).
  • 93
    • 33644910852 scopus 로고    scopus 로고
    • note
    • 8-methyl substituent by a hydrogen atom, is restricted to the intramolecular cyclization step. The complete catalytic cycle for the IHC of 1x in the presence of precatalyst 2 will be reported elsewhere.
  • 94
    • 33644892723 scopus 로고    scopus 로고
    • note
    • b) Under identical reaction conditions, as for substrate 1 (see ref. [9c]), a 10:90 ratio of 5-exo-(2-vinylpyrrolidine)/6-endo-(2- methyltetrahydropyridine) products is observed for the IHC of 1x in the presence of 2 (see ref. [9a,c]).
  • 95
    • 33644917651 scopus 로고    scopus 로고
    • note
    • Substrate adducts 4-S with a disrupted azacycle - Lu interaction are energetically unfavorable. For more details see the Supporting Information.
  • 96
    • 33644924270 scopus 로고    scopus 로고
    • note
    • 7 carbon of 5 is predicted to be kinetically less likely than the path commencing from 5′ (see Table S2 and Figure S5 of the Supporting Information).
  • 97
    • 33644905502 scopus 로고    scopus 로고
    • note
    • 3-allylic - Lu interaction in Ss′-S remains essentially intact (see Figure S6 of the Supporting Information).
  • 99
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    • note
    • In the comparison of the energetics of the alternative regioisomeric pathways, the respective favorable stereochemical pathways were considered.
  • 100
    • 33644880196 scopus 로고    scopus 로고
    • note
    • -1 on consideration of real reaction conditions (70 molar excess of 1, 298.15 K, 1 atm (see ref. [9d]).
  • 102
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    • note
    • b) Intermediates 4a and 4s are likely to be transient species and are thus present in negligible stationary concentrations because their formation through reversible 3′→4a/4s 5-exo cyclization and ensuing 4a/4s+1→4a-S/4s-S substrate association are facile processes.
  • 103
    • 33644906865 scopus 로고    scopus 로고
    • note
    • tot) are given relative to the catalyst's resting state 3′-S, and are corrected by the respective number of substrate molecules.
  • 104
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    • note
    • -1.
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    • The reader is referred to Baldwin's rules for ring closure which predict both exo- and endocyclic paths to be favorable for aminoallenes, while for aminodienes only the exocyclic path is predicted to be favorable. See: J. March, Advanced Organic Chemistry, 4th ed., Wiley, New York, 1992, pp. 212-214.
    • (1992) Advanced Organic Chemistry, 4th Ed. , pp. 212-214
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    • note
    • -1 (298.15 K).
  • 107
    • 33644903721 scopus 로고    scopus 로고
    • note
    • -1 (see ref. [21b]).


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.