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0001195856
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4)(R-pybox)] complexes, iPr-pybox complex has been found to be much more active and selective than the Ph-pybox analogues; according to ref. [14k]: copper(I)-Ph-pybox complexes are more active and enantioselective catalysts in the addition of terminal alkynes to imines than the corresponding iPr-pybox analogues.
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60
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0842295483
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note
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3 at 40°C in dichloromethane for 1 h (35% yield) (unpublished results from this laboratory).
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61
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0842273768
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note
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For complexes containing the allyl-substituted phosphines an im-provement in performance has been obtained by adding the base 10 min before the ketone (entry 3 vs 2). This fact may be explained by assuming an isomerisation of the allyl group in the presence of base, which may occur before the chloride abstraction from the metal. Therefore, the active species probably contain diphenyl(2-methylvinyl)phosphine.
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62
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0842295480
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note
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Pathways that favour the reverse reaction leading to loss of ee cannot be discarded either.
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63
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0842273772
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note
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We have found that a base/catalyst of ca. 24:1 leads to better conversions for these substrates, in contrast to the ratio (ca. 6:1) found for acetophenone.
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64
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0036605676
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For a short review and mechanistic studies see: a) J.-E. Bäckvall, J. Organomet. Chem. 2002, 652, 105-111;
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Bäckvall, J.-E.1
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66
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0842273773
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note
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The dissociation of the coordinated phosphine or phosphite has to be discarded; otherwise, no influence on ee values would be observed.
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67
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0000898101
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Y. Nishibayashi, I. Takei, S. Uemura, M. Hidai, Organometallics 1999, 18, 2291-2293.
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Nishibayashi, Y.1
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Hidai, M.4
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68
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0842273774
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note
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From Aldrich 2003-2004: (R,R)-Ph-pybox (49606-5); (S,S)-Ph-pybox (49607-3). From TCI 2003: (R,R)-Ph-pybox (B2219); (S,S)-Ph-pybox (B2220).
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