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73349135136
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For two noteworthy applications to natural product synthesis wherein the reversible nature of catalytic cross-metathesis is utilized, see
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For two noteworthy applications to natural product synthesis wherein the reversible nature of catalytic cross-metathesis is utilized, see :
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5 indicates that RCM of this class of dienes with Ru-based carbenes leads to the formation of a mixture of E and Z isomers. Such observations suggest that, in contrast to the initial suppositions (ref. [4c]), the high Z-selectivity obtained in the reaction illustrated in Scheme 1 is largely imposed by the Mobased alkylidene (vs the conformational preferences of the substrate). See
-
5 indicates that RCM of this class of dienes with Ru-based carbenes leads to the formation of a mixture of E and Z isomers. Such observations suggest that, in contrast to the initial suppositions (ref. [4c]), the high Z-selectivity obtained in the reaction illustrated in Scheme 1 is largely imposed by the Mobased alkylidene (vs the conformational preferences of the substrate). See: E. Llàcer, F. Urpì J. Vilarrasa, Org. Lett. 2009, 11, 3198-3201.
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0032569168
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For examples of these types of total syntheses reported from our laboratories, see: a ring-opening/cross-metathesis: cross-metathesis
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For examples of these types of total syntheses reported from our laboratories, see: a) ring-opening/cross-metathesis: C.W. Johannes, M. S. Visser, G. S. Weatherhead, A. H. Hoveyda, J. Am. Chem. Soc. 1998, 120, 8340-8347;cross-metathesis:
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enyne ring-closing metathesis
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73349086048
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Formation of macrocyclic 11 is a rare example of an endoselective processes catalyzed by Ru-based complex; Ru-based carbenes, unlike Mo alkylidenes, typically deliver the corresponding exo-dienes. For endo- and enantioselective Mo-catalyzed enyne RCM reactions, see
-
Formation of macrocyclic 11 is a rare example of an endoselective processes catalyzed by Ru-based complex; Ru-based carbenes, unlike Mo alkylidenes, typically deliver the corresponding exo-dienes. For endo- and enantioselective Mo-catalyzed enyne RCM reactions, see:
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There has been one report of control of planar stereogenicity through Mo-catalyzed enantioselective RCM. See
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There has been one report of control of planar stereogenicity through Mo-catalyzed enantioselective RCM. See: M. Ogasawara, S. Watanabe, L. Fan, K. Nakajima, T. Takahashi, Órganometallics 2006, 25, 5201-5203.
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For representative examples of catalytic enantioselective additions of C-based nucleophiles to ketones, see
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For representative examples of catalytic enantioselective additions of C-based nucleophiles to ketones, see:
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Formation of an all-carbon quaternary stereogenic center through enantioselective olefin metathesis is relatively rare. For the first example of such a transformation, see
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Formation of an all-carbon quaternary stereogenic center through enantioselective olefin metathesis is relatively rare. For the first example of such a transformation, see: A.-L. Lee, S. J. Malcolmson, A. Puglisi, R. R. Schrock, A. H. Hoveyda, J. Am. Chem. Soc. 2006, 128, 5153-5157.
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Most recently, another application of enantioselective Ru-catalyzed RCM reactions to natural product synthesis has been reported. See
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s lead to formation of substantial amounts of oligomerization; the desired ROCM products are isolated in only 12-30% yield (A. R. Zhugralin, M. Yu, A. H. Hoveyda, unpublished results). The mechanistic details for the difference in efficiencies of these two classes of Ru-based carbenes in promoting ROCM reactions will be disclosed shortly in a separate account.
-
s lead to formation of substantial amounts of oligomerization; the desired ROCM products are isolated in only 12-30% yield (A. R. Zhugralin, M. Yu, A. H. Hoveyda, unpublished results). The mechanistic details for the difference in efficiencies of these two classes of Ru-based carbenes in promoting ROCM reactions will be disclosed shortly in a separate account.
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s originally designed for Ru-catalyzed olefin metathesis have been used to promote other classes of transformations. See: (Cu-catalyzed enantioselective conjugate additions) a
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s originally designed for Ru-catalyzed olefin metathesis have been used to promote other classes of transformations. See: (Cu-catalyzed enantioselective conjugate additions) a)K-s. Lee, M. K. Brown, A. H. Hoveyda, J. Am. Chem. Soc. 2006, 128, 7182-7184;
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For other chiral, stereogenic-at-Ru, catalysts that have been used in olefin metathesis but only in the racemic form, see : a
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For other chiral, stereogenic-at-Ru, catalysts that have been used in olefin metathesis but only in the racemic form, see : a) A. Fürstner, M. Liebl, C. W. Lehmann, M. Picquet, R. Kunz, C. Bruneau, D. Touchard, P. H. Dixneuf, Chem. Eur. J. 2000, 6, 1847-1857;
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more..
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K. E. Murphy, A. H. Hoveyda, unpublished results.
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