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33644897275
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-
For further details, see: www.struked.de.
-
-
-
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87
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-
33644889864
-
-
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
-
-
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.
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Hong, S.1
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89
-
-
33644907421
-
-
note
-
Examination by a linear-transit approach gave no indication that this process is associated with a significant enthalpic barrier.
-
-
-
-
91
-
-
33644889863
-
-
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].
-
-
-
-
92
-
-
33644906074
-
-
note
-
The located adduct species 3″-S is characterized by only a weak amidoallene - Ln chelating interaction (cf. Figure S3).
-
-
-
-
93
-
-
33644910852
-
-
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
-
-
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
-
-
note
-
Substrate adducts 4-S with a disrupted azacycle - Lu interaction are energetically unfavorable. For more details see the Supporting Information.
-
-
-
-
96
-
-
33644924270
-
-
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
-
-
note
-
3-allylic - Lu interaction in Ss′-S remains essentially intact (see Figure S6 of the Supporting Information).
-
-
-
-
98
-
-
0039785339
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H. M. Senn, P. E. Blöchl, A. Togni, J. Am. Chem. Soc. 2000, 122, 4098.
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Senn, H.M.1
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99
-
-
33644905501
-
-
note
-
In the comparison of the energetics of the alternative regioisomeric pathways, the respective favorable stereochemical pathways were considered.
-
-
-
-
100
-
-
33644880196
-
-
note
-
-1 on consideration of real reaction conditions (70 molar excess of 1, 298.15 K, 1 atm (see ref. [9d]).
-
-
-
-
102
-
-
33644891280
-
-
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
-
-
note
-
tot) are given relative to the catalyst's resting state 3′-S, and are corrected by the respective number of substrate molecules.
-
-
-
-
104
-
-
33644889312
-
-
note
-
-1.
-
-
-
-
105
-
-
0003467672
-
-
Wiley, New York
-
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.
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-
-
March, J.1
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106
-
-
33644910377
-
-
note
-
-1 (298.15 K).
-
-
-
-
107
-
-
33644903721
-
-
note
-
-1 (see ref. [21b]).
-
-
-
|