(+)-Trienomycins A, B, and C: relative and absolute stereochemistry

Smith, Amos B.; Wood, John L.; Wong, Weichyun; Gould, Alexandra E.; Rizzo, Carmelo J.; Funayama, Shinji; Ōmura, Satoshi

doi:10.1021/ja00176a070

Cited by 30 publications

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“…The most potent molecule, (+)-trienomycin A ( 1a , Figure ), along with (+)-mycotrienin I ( 1c ) and II ( 1e ) and the mycotrienols II ( 1d , f ) have previously been isolated from the fermentation broth of the Streptomyces rishirensis. Their relative and absolute stereochemistries have been determined by Smith and co-workers through careful degradative and spectroscopic methods . A stereoview of a minimized (+)-mycotrienin I ( 1c ) illustrating its various structural elements is shown in Figure…”

Section: Introductionmentioning

confidence: 99%

Total Synthesis of (+)-Mycotrienol and (+)-Mycotrienin I: Application of Asymmetric Crotylsilane Bond Constructions

et al. 1998

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A highly convergent asymmetric synthesis of the ansamycin antibiotics (+)-mycotrienin I (1c) and (+)-mycotrienol (1d) has been achieved through the synthesis and coupling of the C9−C16 subunit 3b and the aromatic subunit 4b, respectively. This article describes the complete details of that work as it illustrates the utility of our developing chiral (E)-crotylsilane bond construction methodology in total synthesis. All four stereogenic centers were introduced using chiral allylsilane bond construction methodology. In the synthesis of subunit 3b, the C12 and C13 stereocenters were installed using an asymmetric crotylsilylation reaction to α-keto dibenzyl acetal 5. The C11 stereocenter was subsequently installed via a chelate-controlled addition of allyltrimethylsilane to establish the anti-1,3-diol system. The C14−C15 trisubstituted double bond was then installed via a reductive opening of α,β-unsaturated lactone 10b. Aromatic subunit 4b was chosen on the basis of its synthon equivalency to the amidobenzoquinone system of (+)-1c and (+)-1d. Subunit 4b was constructed in a concise six-step sequence which incorporates the C3 stereogenic center of the C1−C5 side chain. The C3 stereogenic center was established using a Weinreb amidation of aniline 18 with lactone (+)-16, whose absolute stereochemistry was derived using the crotylsilane methodology. The union of subunit 3b with aromatic subunit 4b was accomplished using a sulfone-based coupling strategy. Coupling product 21 was transformed through a sequence of steps to triene 24. Divergence from this advanced intermediate allows access to both natural products. The successful completion of the synthesis included the incorporation of the (E,E,E)-triene unit with simultaneous macrocyclization through a palladium (0)-catalyzed (Stille-type) coupling macrocyclization.

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Section: Introductionmentioning

confidence: 99%

Total Synthesis of (+)-Mycotrienol and (+)-Mycotrienin I: Application of Asymmetric Crotylsilane Bond Constructions

et al. 1998

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“…As a prelude to total synthesis, we have elucidated the complete relative and absolute configurations for (+)-trienomycins A−C ( 1 − 3 ) and (+)-mycotrienins I and II ( 6 and 7 ) as well as the development of an end-game synthetic strategy for elaboration of the trienomycins from a common advanced intermediate, (+)-trienomycinol ( 14 ) .…”

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confidence: 99%

(+)-Trienomycins A, B, C, and F and (+)-Mycotrienins I and II: Relative and Absolute Stereochemistry

et al. 1996

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“…Additionally, HPLC profiling of these extracts indicated the presence of secondary metabolites with UV absorptions consistent with the ansamycins (λ max 214 and 272 nm). Chemical investigation led to the isolation of two new benzenic ansamycins, trienomycins H ( 1 ) and I ( 2 ), along with the known trienomycinol ( 3 ) [ 36 , 37 ] ( Figure 1 ). The trienomycins A–F [ 29 , 38 , 39 ] possess different N -acyl substituted alanine ester moieties attached to C-11 of the ansamycin-like ring, such as cyclohexanecarboxyl, 3-methylbutanoyl, ( S )-2-methylbutanoyl, 1-cyclohexene-1-carboxyl, 4-methylpentanoyl, ( E )-3-pentenoyl, and ( E )-2-methyl-2-butenoyl, respectively, while the trienomycin G [ 21 ] is the isomer of trienomycin A by interchanging the position of 11- and 13- substituents.…”

Section: Introductionmentioning

confidence: 99%

New Ansamycins from the Deep-Sea-Derived Bacterium Ochrobactrum sp. OUCMDZ-2164

et al. 2018

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Two new ansamycins, trienomycins H (1) and I (2), together with the known trienomycinol (3), were isolated from the fermentation broth of the deep-sea-derived bacterium Ochrobactrum sp. OUCMDZ-2164. Their structures, including their absolute configurations, were elucidated based on spectroscopic analyses, ECD spectra, and Marfey’s method. Compound 1 exhibited cytotoxic effects on A549 and K562 cell lines with IC50 values of 15 and 23 μM, respectively.

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(+)-Trienomycins A, B, and C: relative and absolute stereochemistry

Cited by 30 publications

References 0 publications

Total Synthesis of (+)-Mycotrienol and (+)-Mycotrienin I: Application of Asymmetric Crotylsilane Bond Constructions

Total Synthesis of (+)-Mycotrienol and (+)-Mycotrienin I: Application of Asymmetric Crotylsilane Bond Constructions

(+)-Trienomycins A, B, C, and F and (+)-Mycotrienins I and II: Relative and Absolute Stereochemistry

New Ansamycins from the Deep-Sea-Derived Bacterium Ochrobactrum sp. OUCMDZ-2164

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