A Flexible and Divergent Strategy to Flavonoids with a Chiral A-Ring Featuring Intramolecular Michael Addition: Stereoselective Synthesis of (+)-Cryptocaryone, (+)-Cryptogione F, and (+)-Cryptocaryanones A and B, as Well as (+)-Cryptochinones A and C

Liu, Xiaojing; Jia, Junhao; Jia, Yuanliang; He, Gu; Luo, Jingwen; Chen, Xiaochuan

doi:10.1021/acs.orglett.8b00479

Cited by 16 publications

(2 citation statements)

References 41 publications

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“…However, Morita–Baylis–Hillman reaction is not employed to construct the hydroxylated cyclohexenyl rings of the C7-carbasugars yet. For the past several years we have been engaged in developing new synthetic routes of some natural products and bioactive analogues featuring regioselective and stereoselective cyclization reactions . In continuation of our synthetic interest in gabosines and related analogues, ,, we report a new approach to several C7-cyclitols including carbasugar ester 1 , epicorepoxydon A, epoxydines B and C via a stereoselective Morita–Baylis–Hillman cyclization.…”

Section: Introductionmentioning

confidence: 99%

A Synthetic Approach to Several C7-Carbasugars via a Key Intramolecular Morita–Baylis–Hillman Reaction

Jia

Wang

et al. 2022

J. Org. Chem.

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A new synthetic strategy for C7-carbasugars is developed via an intramolecular Morita−Baylis−Hillman reaction, in which a substituted dial precursor prepared from D-mannose cyclizes smoothly in the presence of DMAP to afford polyhydroxylated cyclohex-1-enecarbaldehyde with good yield. By employment of the cyclization products as key intermediates, the first syntheses of carbasugar ester 1 and epicorepoxydon A, as well as practical syntheses of epoxydines B and C, (−)-MK7607, (−)-streptol, and (−)-gabosine E are achieved.

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Section: Introductionmentioning

confidence: 99%

A Synthetic Approach to Several C7-Carbasugars via a Key Intramolecular Morita–Baylis–Hillman Reaction

Jia

Wang

et al. 2022

J. Org. Chem.

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“…Optically active epoxides and vicinal diols are versatile synthons for the synthesis of high-value compounds that are widely applied in the pharmaceutical, agrochemical, and fine chemical industries . For example, ( S )-styrene oxide ( 1a ) was utilized for the synthesis of KDM1A inhibitors, flavonoid (+)-cryptocaryanone A or cryptochinone C, and alkaloid (+)-sedamine or allosedamine, while ( R )-phenylethane-1,2-diol ( 1b ) was used for NK-1 receptor antagonists (+)-CP-99,994 and (+)-CP-122,721 and syncarpamide . ( S )- p -Nitro-, chloro-, and fluoro-styrene oxides ( 2a , 5a , and 8a ) were used for the synthesis of neuroprotective agents, − ( R )-glycidyl ethers ( 11a – 14a ) for polyesters, ( S )-1,2-epoxyhexane ( 18a ) for umuravumbolide, and ( S )-1,2-epoxyoctane ( 19a ) for chamuvarinin .…”

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confidence: 99%

Structure-Guided Regulation in the Enantioselectivity of an Epoxide Hydrolase to Produce Enantiomeric Monosubstituted Epoxides and Vicinal Diols via Kinetic Resolution

Hou

et al. 2022

Org. Lett.

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Structure-guided microtuning of an Aspergillus usamii epoxide hydrolase was executed. One mutant, A214C/A250I, displayed a 12.6-fold enhanced enantiomeric ratio (E = 202) toward rac-styrene oxide, achieving its nearly perfect kinetic resolution at 0.8 M in pure water or 1.6 M in n-hexanol/water. Several other beneficial mutants also displayed significantly improved E values, offering promising biocatalysts to access 19 structurally diverse chiral monosubstituted epoxides (97.1 – ≥ 99% ees) and vicinal diols (56.2–98.0% eep) with high yields.

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Temperature‐Controlled Stereodivergent Synthesis of 2,2′‐Biflavanones Promoted by Samarium Diiodide

Soto

Soengas

Silva

et al. 2019

Chemistry A European J

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In this work,t he first exampleo faradical stereodivergent reactiond irected towardst he stereoselective synthesis of both (R*,R*)-and (R*,S*)-2,2'-biflavanones promoted by samarium diiodide is reported. Control experiments showedt hat the selectivity of this reaction was exclusively controlled by the temperature. It was possible to generate av ariety of 2,2'-biflavanones bearing different substitution patterns at the aromatic ring in good-toquantitative yields, being both stereoisomerso ft he desired compounds obtained with total or high control of selectivity.Amechanismt hat explains both the generation of the corresponding 2,2'-biflavanones and the selectivity is also discussed. The structure ands tereochemistry determination of each isomer was unequivocally elucidatedb y single-crystal X-ray diffraction experiments.Flavonoid-derivedc ompounds are gainingi ncreasinga ttention owing to their interesting biological activity,i ncluding their anticarcinogenic, antifungal, antiviral,a ntibacterial,a ntimicrobial, antioxidant, anxiolytic and anti-inflammatory properties. For this reason, several methodsd irected towards the stereoselective synthesis of flavonoid-related compounds, includingb iflavonoids, have been recently published. [1] Despite the large number of biflavonoids that are suggestedt oe xist in nature, only ac ouple of dozen naturalb iflavonoidsh ave been explored for biological activity studies. In this respect, it has also been shown that, in general terms, the dimerization of flavonoid units is av aluable protocol for the synthesis of biflavonoids, being the bioactivity of these compounds remarkably increased when compared with that shown by the flavonoid monomer. [2] For all these reasons, the developmento fn ew stereoselectives ynthetic proceduresa imed the synthesis of bifla-vonoidsa re of great interesti no rganic synthesis. Moreover,a s part of an ongoing project on the synthesis and biological evaluation of phenolic compounds, we became also interested in the efficient preparation of 2,2'-biflavonoids. For this purpose,w ee nvisioned the reductive coupling of 4-oxo-4H-1-benzopyrans,t hrough their 2-positions,b ym eans of samarium diiodideasasingle-electron transfer (SET) reagent.Samarium diiodide [3] is unique when compared with other SET reagents given its well-known high versatility in providing different radicals in organic synthesis.I nfact, the use of samarium diiodide has been widely covered in the literature in different reductivep rocesses, [4] including homo-or heterocoupling reactions. [5] Our group has accumulated aw idee xperience in the use of samarium diiodidei nb oth ionic and radicalr eactions,i ncluding its application in 1,2-elimination processes, [6] cyclopropanation reactions [7] reduction of multiple bonds [8] and the stereoselective synthesis of compounds of high value derived from naturalp roducts such as carbohydrates [9] or aaminoa cids. [10] Encouraged by the pharmacological interest in biflavonoids, [1f] hereinw er eport the use of different easily availablef l...

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A Flexible and Divergent Strategy to Flavonoids with a Chiral A-Ring Featuring Intramolecular Michael Addition: Stereoselective Synthesis of (+)-Cryptocaryone, (+)-Cryptogione F, and (+)-Cryptocaryanones A and B, as Well as (+)-Cryptochinones A and C

Cited by 16 publications

References 41 publications

A Synthetic Approach to Several C7-Carbasugars via a Key Intramolecular Morita–Baylis–Hillman Reaction

A Synthetic Approach to Several C7-Carbasugars via a Key Intramolecular Morita–Baylis–Hillman Reaction

Structure-Guided Regulation in the Enantioselectivity of an Epoxide Hydrolase to Produce Enantiomeric Monosubstituted Epoxides and Vicinal Diols via Kinetic Resolution

Temperature‐Controlled Stereodivergent Synthesis of 2,2′‐Biflavanones Promoted by Samarium Diiodide

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