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Hydroamination of 1,1-disubstituted alkenes has been reported by Molander;8i however, hydroamination of 1,2-disubstituted alkenes with the same catalyst was not successful.
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77
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For example, the scope of enantioselective intramolecular hydroamination/cyclization by chiral organolanthanide was previously limited to monosubstituted alkenes, affording only methyl substituted chiral azacycles.
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2)) is estimated to be - 12 kcal/mol (±0.6).
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0347538384
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note
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Presumably, two possible conformers (pseudoequatorial or pseudoaxial propenyl) exist which interconvert slowly on the NMR time scale; therefore, some peaks appear as a pair.
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For examples of separation of racemates using an (S,S)-Whelk O1 column, see: (a) Pirkle, W. H.; Welch, C. J. Tetrahedron: Asymmetry 1994, 5, 777-780.
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For an example of separation of 2-substituted piperidines. see: (c) Hyun, M. H.; Jin, J. S.; Lee, W. Bull. Korean Chem. Soc. 1997, 18, 336-339.
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99
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0348168158
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note
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See the Supporting Information for aminodiene substrate synthesis.
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-
-
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100
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0346907579
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note
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Hydroamination/cylization of monosubstituted allenylamines affords mixtures of endo- and exo-cyclization regioisomers, whereas 1,3-disubstituted allenylamines exclusively yield the exo-cyclization product. See ref 11b.
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105
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33845379315
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Jeske, G.; Schock, L. E.; Mauermann, H.; Swepston, P. N.; Schumann, H.; Marks, T. J. J. Am. Chem. Soc. 1985, 107, 8103-8110.
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106
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84944648082
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Representative eight-coordinate effective ionic radii: La(III), 1.160 Å: Nd(III), 1.109 Å; Sm(III), 1.079 Å; Y(III), 1.019 Å; Yb(III), 0.985 Å; Lu(III), 0.977 Å. See: Shannon, R. D. Acta Crystallogr., Sect. A 1976, A32, 751-767.
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Shannon, R.D.1
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107
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0346907549
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note
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Relative stereochemistry confirmed by NOESY experiments and derivatization.
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-
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108
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0033525637
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and references therein
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Kirihara, M.; Nishio, T.; Yokoyama, S.; Kakuda, H.; Momose, T. Tetrahedron 1999, 55, 2911-2926 and references therein.
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Kirihara, M.1
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109
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0346277349
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Boston, MA; August; American Chemical Society: Washington, DC, 2002; abstract INOR 668
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(a) Hong, S.; Ryu, J-.S.; Tian, S.; Metz, M. V.; Marks, T. J. Abstracts of Papers; communicated in part at the 224th National ACS Meeting, Boston, MA; August 2002; American Chemical Society: Washington, DC, 2002; abstract INOR 668.
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Abstracts of Papers; Communicated in Part at the 224th National ACS Meeting
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Hong, S.1
Ryu, J.-S.2
Tian, S.3
Metz, M.V.4
Marks, T.J.5
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111
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0000550667
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and references therein for other recent syntheses
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For the catalytic asymmetric synthesis of coniine via imine hydrosilylation, see: Reding, M. T.; Buchwald, S. L. J. Org. Chem. 1998, 63, 6344-6347 and references therein for other recent syntheses.
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Reding, M.T.1
Buchwald, S.L.2
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112
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0035944472
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Organolanthanide-catalyzed hydrophosphinations exhibit similar but more pronounced kinetic inhibition effects, depending upon the steric bulk of the product. See: Douglass, M. R.; Stern, C. L.; Marks. T. J. J. Am. Chem. Soc. 2001, 123, 10221-10238.
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Douglass, M.R.1
Stern, C.L.2
Marks, T.J.3
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115
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0348168118
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note
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Parameters in parentheses represent 3σ values derived from the least-squares fit.
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116
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0346907548
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note
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Methyl substitution leads to a destabilization of the proposed transition state C relative to R = H or Ph; however, a reversed H versus Ph substituent effect for two different lanthanide catalysts appears to imply competing steric effects as well.
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117
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0001247165
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BINAP = 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl: Noyori, R.; Takaya, H. Acc. Chem. Res. 1990, 23, 345-350.
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Noyori, R.1
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Loiseleur, O.; Hayashi, M.; Schmees, N.; Pfaltz, A. Synthesis 1997, 1338-1345.
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Loiseleur, O.1
Hayashi, M.2
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Pfaltz, A.4
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119
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0347538383
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note
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1H NMR,9b and epimerization of chiral lanthanocene catalysts in the presence of amines.9a-c For other related examples, see footnote 38 in ref 10a.
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-
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120
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0346277350
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note
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2SiCp″(CpR*)Ln catalysts (Ln = Nd, Sm) reveal that the product resonances are often broadened after ∼1 half-life, which implies that the product heterocycles are significantly involved in coordination to/amine exchange with the chiral paramagnetic lanthanide amine-amido complexes.9b
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122
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0003518480
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Wiley: New York, Chapters 1-3
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(b) Segel, I. H. Enzyme Kinetics; Wiley: New York, 1975; Chapters 1-3.
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Enzyme Kinetics
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Segel, I.H.1
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123
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0346277351
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note
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3+ for aminoallene cyclizations.
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