Enantioselective total synthesis of (+)-vincamine

Xue, Fei; Liu, Hengmao; Wang, Rui; Zhang, Dan; Song, Hao; Liu, Xiaoyu; Qin, Yong

doi:10.1016/j.cclet.2021.09.032

Cited by 6 publications

(3 citation statements)

References 69 publications

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“…We opted to investigate the Bischler–Napieralski/reduction sequence aiming to find the optimal conditions for high efficiency and diastereoselectivity. As the protocols described by Takano , and Schlessinger led to decomposition of 19 , we turned our attention to the milder conditions introduced by Movassaghi . Bischler–Napieralski cyclization of 19 proceeded smoothly with a combination of triflic anhydride and 2-chloropyridine.…”

Section: Resultsmentioning

confidence: 99%

Streamlined Strategy for Scalable and Enantioselective Total Syntheses of the Eburnane Alkaloids

Ramakrishna,

Pop,

Latif

et al. 2023

J. Am. Chem. Soc.

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Section: Resultsmentioning

confidence: 99%

Streamlined Strategy for Scalable and Enantioselective Total Syntheses of the Eburnane Alkaloids

Ramakrishna,

Pop,

Latif

et al. 2023

J. Am. Chem. Soc.

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“…Hence, we speculated that the diastereoselectivity of this transformation could be closely related to the inherent nature of the substrate, thereby increasing the steric bulk of the R group attached to C20 and favoring cis -selectivity. Persisting with our efforts on the total syntheses of the eburnamine-vincamine alkaloids, , we disclose our second-generation asymmetric hydrogenation/desymmetrizing lactamization cascade with excellent control of both the enantioselectivity and C20/C21 cis -selectivity (up to 98% ee , >20:1 dr ) when the bulky-R substrates are employed. The encouraging outcome of this study led us to move forward with the syntheses of the C18-oxo eburnamine-vincamine alkaloids.…”

mentioning

confidence: 98%

“… The core structures of these alkaloids share a unique pentacyclic skeleton containing an indolo[2,3- a ]quinolizine moiety and two consecutive stereogenic centers at the C20/C21 positions, thus resulting in a cis -fused D/E ring system. Such a structural/stereochemical feature coupled with an array of outstanding pharmacological properties has prompted substantial investigations on the chemical syntheses of these alkaloids, which have been widely exploited for both natural and semisynthetic drug discovery and development efforts …”

mentioning

confidence: 99%

Stereoselective Total Syntheses of C18-Oxo Eburnamine-Vincamine Alkaloids

et al. 2022

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Here, we disclose the divergent total syntheses of representative C18-oxo eburnamine-vincamine alkaloids (+)-eburnaminol, (−)-larutenine, and (−)-cuanzine. Key to the approach is a substrate-controlled iridium-catalyzed asymmetric hydrogenation/lactamization cascade that leads to the formation of the common tetracyclic skeleton with essential cis-C20/C21 stereochemistry (93% yield, 98% ee, >20:1 dr, gram scale). Access to the targeted alkaloids is effected late in the synthesis by implementation of a number of diversity-oriented transformations and late-stage modifications.

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Catalytic Enantioselective Construction of 6‐4 Ring‐Junction All‐Carbon Stereocenters and Mechanistic Insights

Wang

et al. 2022

Chin. J. Chem.

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Comprehensive Summary Developing reactions for the synthesis of 6‐6‐4 and 6‐4 carbocyclic scaffolds with a chiral quaternary center at the bridgehead position is highly desired, considering the existence of such skeletons in natural products with biological activities and the potential of using these molecules for downstream studies in chemical biology and medicinal chemistry. Report here is accessing these target skeletons with high chemo‐, regio‐ and enantio‐selectivities through Pd(II)/chiral N,N’‐disulfonyl bisimidazoline (Bim) ligand‐catalyzed asymmetric reaction of yne‐allenones and arylboronic acids. Realization of 6‐6‐4 skeleton with a ring‐junction all‐carbon stereocenter is a one‐step process while synthesizing 6‐4 skeleton is a two‐step process, which begins with intramolecular [2 + 2] reaction of allenes with alkynes, followed by Pd‐catalyzed asymmetric addition of arylboronic acids to cyclic enones generated in the first step. Noteworthy is that chiral Bim ligand as a C2‐symmetric N,N’‐bidentateanionic ligand, designed by us, in coordinating with Pd catalyst was first applied to catalyze asymmetric 1,4‐conjugate addition reaction with the high catalytic performance (the reaction can be carried out in air). DFT calculations have been applied to understand how these reactions take place, the origins of enantioselectivity, and relative reactivities of different substrates.

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Enantioselective total synthesis of (+)-vincamine

Cited by 6 publications

References 69 publications

Streamlined Strategy for Scalable and Enantioselective Total Syntheses of the Eburnane Alkaloids

Streamlined Strategy for Scalable and Enantioselective Total Syntheses of the Eburnane Alkaloids

Stereoselective Total Syntheses of C18-Oxo Eburnamine-Vincamine Alkaloids

Catalytic Enantioselective Construction of 6‐4 Ring‐Junction All‐Carbon Stereocenters and Mechanistic Insights

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