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33646502193
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note
-
All kinetic runs were performed in triplicate to ensure accuracy and reproducibility. See the Supporting Information for complete details.
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32
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33646525015
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36
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33646522459
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note
-
It should be noted that methyl ketone derived trichlorosilyl enolates are less reactive than the cyclohexanone derived enolate 4. In a control experiment, the trichlorosilyl enolate derived from methyl n-butyl ketone and 4-phenylbenzaldehyde were stirred at -78 °C for 2 h, providing only 4% of the corresponding aldol adduct, with 95% recovery of the unchanged aldehyde after column chromatography.
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For X-ray crystallographic studies of phosphoramides with tin tetrachloride, see ref 11a.
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33646496628
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(d) For an in depth discussion of the design, construction and application of the RINMR apparatus, see ref 10b.
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55
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33646533616
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13C KIEs from NMR integrations and error analysis, see ref 28.
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56
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2 orbitals have the most s-character and therefore are the most electronegative sites. For a description of this bonding scheme, see: Curnow, O. J. J. Chem. Educ. 1998, 75, 910-915.
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33646523436
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- arises from the role of chloride as a competitive ligand for the complex.
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75
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33646499013
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note
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Complexes vi and vii also exist as two limiting diastereomeric chair complexes, but will not be considered at this level of analysis.
-
-
-
-
76
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33646528494
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note
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The octahedral silicon structure is created from two hypervalent (3-center-4-electron) hybrid orbitals and one sp hybrid. For a description of this bonding scheme, see refs 9c and 30.
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77
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The high tendency of group 14 complexes to be cis configured also rules out complex ix. Ruzicka, S. J.; Merbach, A. E. Inorg. Chim. Acta 1976, 20, 221-229.
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33646534666
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note
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+ the silicon has a half share of 9 electrons). It never has to become a very high energy cationic 7 electron species and remains hypervalent and formally electron rich.
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-
-
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79
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33646506663
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note
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We have demonstrated a cooperative effect on the stereoselectivity of aldol additions with acyclic trichlrosilyl enolated using tethered phosphoramides: see ref 6b.
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