3,3′-Bis(trisarylsilyl)-substituted binaphtholate rare earth metal catalysts for asymmetric hydroamination

Journal of the American Chemical Society

Volumn 128, Issue 11, 2006, Pages 3748-3759

  Gribkov, Denis V ^a   Hultzsch, Kai C ^a   Hampel, Frank ^a  

^a UNIVERSITY OF ERLANGEN NUREMBERG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSTS; CONCENTRATION (PROCESS); HYDROCARBONS; PROPYLENE; SILICON COMPOUNDS; STYRENE;

AMINE ELIMINATION; ENANTIOSELECTIVITIES; HYDROAMINATION; METAL CATALYSTS;

RARE EARTH ELEMENTS;

2,2' DIHYDROXY 1,1' BINAPHTHYL; ALKANE; AMINE; LANTHANIDE; LUTETIUM; METAL COMPLEX; NAPHTHOL DERIVATIVE; POLYCYCLIC AROMATIC HYDROCARBON; PROPYLAMINE; SCANDIUM; STYRENE; YTTRIUM; ALKENE; NAPHTHALENE DERIVATIVE; ORGANOMETALLIC COMPOUND;

AMINATION; ARTICLE; CATALYST; CHIRALITY; CONCENTRATION RESPONSE; CRYSTALLOGRAPHY; CYCLIZATION; DIASTEREOISOMER; ELIMINATION REACTION; CATALYSIS; CHEMISTRY;

ALKENES; AMINATION; AMINES; CATALYSIS; METALS, RARE EARTH; NAPHTHALENES; ORGANOMETALLIC COMPOUNDS;

EID: 33645394124     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja058287t     Document Type: Article

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106. 18
107. 3] and (R)-1b did not form a clean product in the absence of THF.
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112. See Supporting Information for details.
113. See X-ray crystallographic analysis of the Mosher amide of 6c in the Supporting Information.
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116. In catalytic and stoichiometric experiments no discrete catalyst species could be observed.
117. 1H NMR signals of the substrate and product remained sharp throughout the catalytic experiments, indicating a significant weaker binding of the aminic bases to the sterically more hindered metallocene complex in comparison to the sterically more accessible binaphtholate catalysts.
118. 9d indicating a substantial binding of the heterocyclic product to the metal center.
119. (a) Other substrate/catalyst combinations can have different binding constants for substrate and product, as the increased rates observed at high conversion in the cyclization of 5b using (R)-2-Y indicate (Figure S8).
120. 30 No decoalescence was observed even at -90 °C.
121. 8b,9b
122. 15a,c,f
123. 30
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135. 8b
136. S are the apparent rate constants for a certain initial substrate concentration. According to the overall rate law in eq 5, they depend on the total base concentration.
137. R[Ln]·t.
138. Additionally, cyclization of racemic 15a with (R)-2-Y proceeded with 11:1 diastereoselectivity up to 50% conversion, but dropped to 3.4:1 at 100% conversion.
139. -1.
140. 15c
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143. (a) As noted above, the cyclization of 5a by (R)-2-Y performed at 25 °C showed a slight sign of curvature (acceleration, see Figures 6 and S5), suggesting that the binding constant of the pyrrolidine product is slightly smaller than that of the aminoalkene.
144. 9d
145. (c) For product inhibition in rare earth metal catalyzed hydrophosphination, see: Douglass, M. R.; Stern, C. L.; Marks. T. J. J. Am. Chem. Soc. 2001, 123, 10221.
146. 15c Molecular modeling studies indicated that the opposite (minor) pyrrolidine enantiomer should form if the olefin approaches from the apical position to an equatorial Ln-N bond. A change of the approach of the olefin was suggested in be responsible for the reversal of product absolute configuration when catalysts with alkyl-substituted bisoxazolinato ligands were used instead of catalysts with aryl-substituted bisoxazolinato ligands.
147. Further kinetic studies will address this subject.
148. The fact that the p-methoxy functionality in substrate 15g is tolerated by (R)-2-Y without detrimental effect on the rate of cyclization can be explained by the remote position of the methoxy substituent.