Asymmetric synthesis of rocaglamides via enantioselective photocycloaddition mediated by chiral brønsted acids
First Claim
1. A method comprising steps of:
- photochemically generating an oxidopyrylium species from a 3-hydroxychromone derivative; and
reacting the oxidopyrylium species with a dipolarophile, wherein the steps of photochemically generating the oxidopyrylium species and of reacting the oxidopyrylium species with a dipolarophile are carried out in the presence of a TADDOL derivative.
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Abstract
The present invention provides a new strategies for the synthesis of compounds of the rocaglamide family and related natural products. The synthetic approach generally involves photochemical generation of an oxidopyrylium species from a 3-hydroxychromone derivative followed by an enantioselective 1,3-dipolar cycloaddition of the oxidopyrylium species to a dipolarophile in the presence of a TADDOL derivative. This approach can be used for the formation of adducts containing an aglain core structure. Methods of the conversion of aglain core structures to aglain, rocaglamide and forbaglin ring systems are also provided. The present invention also relates to the use of rocaglamide/aglain/forbaglin derivatives for the manufacture of medicaments for use in the treatment of cancer or cancerous conditions, disorders associated with cellular hyperproliferation, or NF-κB-dependent conditions.
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Citations
40 Claims
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1. A method comprising steps of:
- photochemically generating an oxidopyrylium species from a 3-hydroxychromone derivative; and
reacting the oxidopyrylium species with a dipolarophile, wherein the steps of photochemically generating the oxidopyrylium species and of reacting the oxidopyrylium species with a dipolarophile are carried out in the presence of a TADDOL derivative. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18)
- photochemically generating an oxidopyrylium species from a 3-hydroxychromone derivative; and
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19. A method for preparing a compound with an aglain core structure, the method comprising steps of:
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producing an oxidopyrylium species (IT) by photoinduced excited state intramolecular proton transfer of a 3-hydroxychromone derivative (I); and reacting the oxidopyrylium species with a dipolarophile (IV) to obtain the aglain core-containing compound (V), wherein compounds (I), (IT), (IV) and (V) have the following chemical structures; - View Dependent Claims (21, 22, 24, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 38, 39, 40)
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20. A method for preparing a compound with an aglain core structure, the method comprising steps of:
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producing an oxidopyrylium species (IIT) by photoinduced excited state intramolecular proton transfer of a 3-hydroxyflavone derivative (II); and reacting the oxidopyrylium species with a dipolarophile (IV) to obtain the aglain core-containing compound (V′
), wherein compounds (II), (IIT), (IV) and (V′
) have the following chemical structures; - View Dependent Claims (23, 33, 37)
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Specification