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Volumn 49, Issue 1, 2010, Pages 34-44

Catalytic enantioselective olefin metathesis in natural product synthesis. Chiral metal-based complexes that deliver high enantioselectivity and more

Author keywords

Enantioselectivity; Homogeneous catalysis; Natural products organometallic chemistry; Olefin metathesis

Indexed keywords

HOMOGENEOUS CATALYSIS; NATURAL PRODUCTS; OLEFIN METATHESIS; ORGANOMETALLIC CHEMISTRY;

EID: 73349084323     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200904491     Document Type: Review
Times cited : (165)

References (98)
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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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    • For examples of these types of total syntheses reported from our laboratories, see: a ring-opening/cross-metathesis: cross-metathesis
    • 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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    • 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: M. Ogasawara, S. Watanabe, L. Fan, K. Nakajima, T. Takahashi, Órganometallics 2006, 25, 5201-5203.
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    • For representative examples where the presence of a Lewis basic amine leads to inhibition of Ru-catalyzed olefin metathesis, see: a
    • For representative examples where the presence of a Lewis basic amine leads to inhibition of Ru-catalyzed olefin metathesis, see: a) K. L. Lee, J. B. Goh, S. F. Martin, Tetrahedron Lett. 2001, 42, 1635 -1638;
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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
    • 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
    • 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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    • Seeref. [10b].
    • Seeref. [10b].
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    • For Ru-catalyzed enyne RCM reactions, see: a
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.