Synthesis of (-)-talaromycin A

Midland, M. Mark; Gabriel, Josef

doi:10.1021/jo00207a053

Cited by 50 publications

(10 citation statements)

References 5 publications

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“…11c The minor enantiomer of the mono-adduct is transformed to the meso -stereoisomer, amplifying the enantiomeric purity of the product. 12 The ability to engage polyols directly in a site-selective manner streamlines synthesis, as it removes steps otherwise required for protecting group installation-removal and it avoids discrete alcohol-to-aldehyde oxidation (Scheme 2). …”

Section: A New Lexicon Of Catalytic Methodsmentioning

confidence: 99%

“…15c In the event, the chromatographically purified iridium precatalyst modified by ( R )-SEGPHOS delivers the product of double crotylation as predominantly 1 of 16 possible stereoisomers due to the aforementioned amplification effect. 12 The resulting pseudo - C 2 -symmetric polypropionate stereoquintet possesses a chirotopic nonstereogenic center at the central carbon atom. Iodoetherification defines this stereocenter and differentiates the two terminal olefin and two secondary alcohol moieties.…”

Section: A New Lexicon Of Catalytic Methodsmentioning

confidence: 99%

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Polyketide construction via hydrohydroxyalkylation and related alcohol C–H functionalizations: reinventing the chemistry of carbonyl addition

et al. 2014

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Despite the longstanding importance of polyketide natural products in human medicine, nearly all commercial polyketide-based drugs are prepared through fermentation or semi-synthesis. The paucity of manufacturing routes involving de novo chemical synthesis reflects the inability of current methods to concisely address the preparation of these complex structures. Direct alcohol C-H bond functionalization via “C-C bond forming transfer hydrogenation” provides a powerful, new means of constructing type I polyketides that bypasses stoichiometric use of chiral auxiliaries, premetallated C-nucleophiles, and discrete alcohol-to-aldehyde redox reactions. Using this emergent technology, the total syntheses of 6-deoxyerythronolide B, bryostatin 7, trienomycins A and F, cyanolide A, roxaticin, and formal syntheses of rifamycin S and scytophycin C, were accomplished. These syntheses represent the most concise routes reported to any member of these respective natural product families.

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Section: A New Lexicon Of Catalytic Methodsmentioning

confidence: 99%

Section: A New Lexicon Of Catalytic Methodsmentioning

confidence: 99%

Polyketide construction via hydrohydroxyalkylation and related alcohol C–H functionalizations: reinventing the chemistry of carbonyl addition

et al. 2014

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“…However, propane-1,3-diol and related glycols are highly tractable and participate in bidirectional allylation via sequential generation and capture of transient monoaldehydes to provide C 2 -symmetric adducts in good yield [286]. In these processes, the minor enantiomer of the monoallylated intermediate is transformed to the meso -stereoisomer of the product, thus amplifying the level of enantiomeric enrichment (Scheme 22) (This mechanism for enantiomeric enrichment is documented by Eliel and Midland: [287, 288]).…”

Section: Iridium-catalyzed Transfer Hydrogenation For C–c Bond Formmentioning

confidence: 99%

Formation of C–C Bonds via Iridium-Catalyzed Hydrogenation and Transfer Hydrogenation

2010

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The formation of C-C bonds via catalytic hydrogenation and transfer hydrogenation enables carbonyl and imine addition in the absence of stoichiometric organometallic reagents. In this review, iridium-catalyzed C-C bond-forming hydrogenations and transfer hydrogenations are surveyed. These processes encompass selective, atom-economic methods for the vinylation and allylation of carbonyl compounds and imines. Notably, under transfer hydrogenation conditions, alcohol dehydrogenation drives reductive generation of organoiridium nucleophiles, enabling carbonyl addition from the aldehyde or alcohol oxidation level. In the latter case, hydrogen exchange between alcohols and π-unsaturated reactants generates electrophile-nucleophile pairs en route to products of hydro-hydroxyalkylation, representing a direct method for the functionalization of carbinol C-H bonds.

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“…This phenomenon provides an opportunity for further enantioenrichment of the final alcohol product, as demonstrated with the typically high levels of enantiopurity (>90% ee) observed for the alcohol products in Table 2 . 22 …”

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confidence: 99%

Enantioselective CuH-Catalyzed Reductive Coupling of Aryl Alkenes and Activated Carboxylic Acids

2016

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A new method for the enantioselective reductive coupling of aryl alkenes with activated carboxylic acid derivatives via copper hydride catalysis is described. Dual catalytic cycles are proposed, with a relatively fast enantioselective hydroacylation cycle followed by a slower diastereoselective ketone reduction cycle. Symmetrical aryl carboxyclic anhydrides provide access to enantioenriched α-substituted ketones or alcohols with excellent stereoselectivity and functional group tolerance.

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Synthesis of (-)-talaromycin A

Cited by 50 publications

References 5 publications

Polyketide construction via hydrohydroxyalkylation and related alcohol C–H functionalizations: reinventing the chemistry of carbonyl addition

Polyketide construction via hydrohydroxyalkylation and related alcohol C–H functionalizations: reinventing the chemistry of carbonyl addition

Formation of C–C Bonds via Iridium-Catalyzed Hydrogenation and Transfer Hydrogenation

Enantioselective CuH-Catalyzed Reductive Coupling of Aryl Alkenes and Activated Carboxylic Acids

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