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Volumn 49, Issue 5, 2010, Pages 881-885

Total synthesis and absolute configuration of macrocidin A, a cyclophane tetramic acid natural product

Author keywords

Asymmetric catalysis; Hydrogenation; Iridium; Natural products; Total synthesis

Indexed keywords

ABSOLUTE CONFIGURATION; ASYMMETRIC CATALYSIS; ASYMMETRIC HYDROGENATION; CYCLOPHANES; DIECKMANN CYCLIZATION; NATURAL PRODUCTS; TETRAMIC ACIDS; TOTAL SYNTHESIS;

EID: 75749116698     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.200906362     Document Type: Article
Times cited : (67)

References (37)
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    • The natural product numbering
    • The natural product numbering.
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    • It is noted that regioisomer 18' underwent the hydrogenation with slightly lower stereoselectivity and in lower yield. A side product was obtained that was derived from tetrahydropyran formation as well as the deacetonization/decarboxylation as shown below. (Figure Presented)
    • It is noted that regioisomer 18' underwent the hydrogenation with slightly lower stereoselectivity and in lower yield. A side product was obtained that was derived from tetrahydropyran formation as well as the deacetonization/decarboxylation as shown below. (Figure Presented)
  • 28
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    • For the hydrogenation of substrates that contain C-I bonding, a report has been published on the tolerance of vinyl iodide to hydrogenation over Crabtree's catalyst
    • For the hydrogenation of substrates that contain C-I bonding, a report has been published on the tolerance of vinyl iodide to hydrogenation over Crabtree's catalyst: R. W. Denton, K. A. Parker, Org. Lett. 2009, 11, 2722-2723.
    • (2009) Org. Lett. , vol.11 , pp. 2722-2723
    • Denton, R.W.1    Parker, K.A.2
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    • The absolute and relative configuration of 19 was verified by Xray analysis at the stage of 24
    • The absolute and relative configuration of 19 was verified by Xray analysis at the stage of 24.
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    • Formation of the disubstituted epoxide is known to be kinetically preferable to formation of the primary epoxide
    • Formation of the disubstituted epoxide is known to be kinetically preferable to formation of the primary epoxide: R. M. Hanson, Org. React. 2002, 60, 1-156.
    • (2002) Org. React. , vol.60 , pp. 1-156
    • Hanson, R.M.1
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    • CCDC 756980 (24) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via
    • CCDC 756980 (24) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www. ccdc.cam.ac.uk/data-request/cif.
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    • For the preparation of phenol 25; see the Supporting Information.
    • For the preparation of phenol 25; see the Supporting Information.
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    • Other protecting groups that were tested but did not allow the final deprotection include: benzyl2,4-dimethoxybenzyl, and 3,4-dimethoxybenzyl groups. This was presumably owing to the susceptibility of the epoxide and the tetramic acid moieties under hydrogenolytic, acidic (TFA), or oxidative (DDQ or cerium ammonium nitrate) conditions
    • Other protecting groups that were tested but did not allow the final deprotection include: benzyl, 2,4-dimethoxybenzyl, and 3,4-dimethoxybenzyl groups. This was presumably owing to the susceptibility of the epoxide and the tetramic acid moieties under hydrogenolytic, acidic (TFA), or oxidative (DDQ or cerium ammonium nitrate) conditions.


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