Enantioselective Total Synthesis of Cymoside through a Bioinspired Oxidative Cyclization of a Strictosidine Derivative

Dou, Yingchao; Kouklovsky, Cyrille; Gandon, Vincent; Vincent, Guillaume

doi:10.1002/ange.201912812

Cited by 11 publications

(1 citation statement)

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“…In comparison with 6‐ O ‐PMB, N ‐Bom protected 3‐amino‐3‐deoxyallal (Scheme 1, II), [20a] an improved diastereoselectivity was obtained for epoxidation/methanolysis of the 6‐ O ‐TBDPS, N ‐Ts protected ADGa 22 a (7.5 : 1 vs. 2.5 : 1, 83 % isolated yield of the methyl 3‐amino‐3‐deoxy‐α‐ d ‐altroside 31 , Scheme 5a) [36] . Tosyl protecting group might have an auspicious effect on the diastereoselectivity of this epoxidation [37] . This assumption is supported by a NOE interaction between H‐2 and the aromatic hydrogen in ortho position of the sulfonamide (Scheme 5b).…”

Section: Resultsmentioning

confidence: 83%

Ferrier/Aza‐Wacker/Epoxidation/Glycosylation (FAWEG) Sequence to Access 1,2‐Trans 3‐Amino‐3‐deoxyglycosides

Geulin

Bourne‐Branchu

Ayed

et al. 2023

Chemistry A European J

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3‐Amino‐3‐deoxyglycosides constitute an essential class of nitrogen‐containing sugars. Among them, many important 3‐amino‐3‐deoxyglycosides possess a 1,2‐trans relationship. In view of their numerous biological applications, the synthesis of 3‐amino‐3‐deoxyglycosyl donors giving rise to a 1,2‐trans glycosidic linkage is thus an important challenge. Even though glycals are highly polyvalent donors, the synthesis and reactivity of 3‐amino‐3‐deoxyglycals have been little studied. In this work, we describe a new sequence, involving a Ferrier rearrangement and subsequent aza‐Wacker cyclization that allows the rapid synthesis of orthogonally protected 3‐amino‐3‐deoxyglycals. Finally a 3‐amino‐3‐deoxygalactal derivative was submitted for the first time to an epoxidation/glycosylation with high yield and great diastereoselectivity, highlighting FAWEG (Ferrier/Aza‐Wacker/Epoxidation/Glycosylation) as a new approach to access 1,2‐trans 3‐amino‐3‐deoxyglycosides.

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Section: Resultsmentioning

confidence: 83%

Ferrier/Aza‐Wacker/Epoxidation/Glycosylation (FAWEG) Sequence to Access 1,2‐Trans 3‐Amino‐3‐deoxyglycosides

Geulin

Bourne‐Branchu

Ayed

et al. 2023

Chemistry A European J

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Total Syntheses of (−)‐Strictosidine and Related Indole Alkaloid Glycosides

et al. 2020

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A collective synthesis of glycosylated monoterpenoid indole alkaloids is reported. A highly diastereoselective Pictet–Spengler reaction with α‐cyanotryptamine and secologanin tetraacetate as substrates, followed by a reductive decyanation reaction, was developed for the synthesis of (−)‐strictosidine, which is an important intermediate in biosynthesis. This two‐step chemical method was established as an alternative to the biosynthetically employed strictosidine synthase. Furthermore, after carrying out chemical and computational studies, a transition state for induction of diastereoselectivity in our newly discovered Pictet–Spengler reaction is proposed. Having achieved the first enantioselective total synthesis of (−)‐strictosidine in just 10 steps, subsequent bioinspired transformations resulted in the concise total syntheses of (−)‐strictosamide, (−)‐neonaucleoside A, (−)‐cymoside, and (−)‐3α‐dihydrocadambine.

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Total Synthesis of Ophiorrhine A, G and Ophiorrhiside E Featuring a Bioinspired Intramolecular Diels–Alder Cycloaddition**

et al. 2022

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We report the first total synthesis of the monoterpene indole alkaloids ophiorrhine A via a late stage bioinspired intramolecular Diels–Alder cycloaddition to form the intricate bridged and spirannic polycyclic system. Several strategies were investigated to construct the indolopyridone moiety of ophiorrhiside E, the postulated biosynthetic precursor of ophiorrhine A. Eventually, the Friedel–Crafts‐type coupling of N‐methyl indolyl‐acetamide with a secologanin‐derived acid chloride delivered ophiorrhine G. Cyclodehydration of a protected form of the latter was followed by the desired spontaneous intramolecular Diels–Alder cycloaddition of protected ophiorrhiside E leading to ophiorrhine A.

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Enantioselective Total Synthesis of Cymoside through a Bioinspired Oxidative Cyclization of a Strictosidine Derivative

Cited by 11 publications

References 61 publications

Ferrier/Aza‐Wacker/Epoxidation/Glycosylation (FAWEG) Sequence to Access 1,2‐Trans 3‐Amino‐3‐deoxyglycosides

Ferrier/Aza‐Wacker/Epoxidation/Glycosylation (FAWEG) Sequence to Access 1,2‐Trans 3‐Amino‐3‐deoxyglycosides

Total Syntheses of (−)‐Strictosidine and Related Indole Alkaloid Glycosides

Total Synthesis of Ophiorrhine A, G and Ophiorrhiside E Featuring a Bioinspired Intramolecular Diels–Alder Cycloaddition**

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