Enantioselective Formal Total Syntheses of Didehydrostemofoline and Isodidehydrostemofoline through a Catalytic Dipolar Cycloaddition Cascade

Fang, Chao; Shanahan, Charles S.; Paull, Daniel H.; Martin, Stephen F.

doi:10.1002/ange.201205274

Cited by 14 publications

(2 citation statements)

References 36 publications

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“…The cage-like stemofoline-type alkaloids, which were considered to be the most complex members of the family, have been persistently pursued in the community. Despite the efforts, only two racemic syntheses were documented by Kende [42] and Overman [43], respectively, until Martin and co-workers accomplished an enantioselective formal synthesis in 2012 [44,45]. In this context, starting from enantiomerically pure 2-deoxy-D-ribose (105), the crucial diazo intermediate 106 was produced via a sequence of transformations over 12 steps (Scheme 15).…”

Section: Stemofoline-typementioning

confidence: 99%

Recent Advances in the Synthesis of Stemona Alkaloids

Liu

Wang

2015

Natural Product Communications

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Stemona alkaloids, featuring polycyclic structures and interesting bioactivities, constitute a distinct class from the Stemonaceae family. In this review, recent advances in the synthesis of these unique alkaloids are briefly discussed, highlighting the application of novel synthetic strategies to access the core structures, as well as creative solutions to the installation of multiple stereogenic centers. The literature reviewed in this article covers the publications from 2010 to November 2014, a period that witnessed the prosperity of the synthesis of Stemona alkaloids.

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Section: Stemofoline-typementioning

confidence: 99%

Recent Advances in the Synthesis of Stemona Alkaloids

Liu

Wang

2015

Natural Product Communications

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“…Starting from stemofoline 38 and (11 Z )-1′,2′-didehydrostemofoline 39 , 40 , several semisynthetic stemofoline alkaloids and analogues have been prepared and screened by Ye et al and Pyne et al, respectively. Although tremendous efforts have been devoted to the total synthesis of these alkaloids 41 – 47 , successful examples remain rare, including racemic total syntheses of isostemofoline ( 2 ) by Kende 48 and didehydrostemofoline (asparagamine A, 3 ) and isodidehydrostemofoline ( 4 ) by Overman 49 , and enantioselective formal total syntheses of didehydrostemofoline and isodidehydrostemofoline by Martin 50 . Notably, although stemofoline ( 1 ) displays remarkable bioactivities, and has proven to be a promising lead for the development of insecticide and anticancer agents, its total synthesis has not yet been achieved.…”

Section: Introductionmentioning

confidence: 99%

Enantioselective total syntheses of (+)-stemofoline and three congeners based on a biogenetic hypothesis

2020

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The powerful insecticidal and multi-drug-resistance-reversing activities displayed by the stemofoline group of alkaloids render them promising lead structures for further development as commercial agents in agriculture and medicine. However, concise, enantioselective total syntheses of stemofoline alkaloids remain a formidable challenge due to their structural complexity. We disclose herein the enantioselective total syntheses of four stemofoline alkaloids, including (+)-stemofoline, (+)-isostemofoline, (+)-stemoburkilline, and (+)-(11S,12R)-dihydrostemofoline, in just 19 steps. Our strategy relies on a biogenetic hypothesis, which postulates that stemoburkilline and dihydrostemofolines are biogenetic precursors of stemofoline and isostemofoline. Other highlights of our approach are the use of Horner–Wadsworth–Emmons reaction to connect the two segments of the molecule, an improved protocol allowing gram-scale access to the tetracyclic cage-type core, and a Cu-catalyzed direct and versatile nucleophilic alkylation reaction on an anti-Bredt iminium ion. The synthetic techniques that we developed could also be extended to the preparation of other Stemona alkaloids.

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Synthesis of (−)‐Pyrido[3,4‐b]homotropane (PHT) and (±)‐PHT via an Intramolecular Cross [3+2] Cycloaddition Strategy

et al. 2018

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An efficient synthesis of (−)‐pyrido[3,4‐b]homotropane (PHT) as well as (±)‐PHT has been achieved in 7 steps from conveniently available starting materials. Key transformations involve an efficient construction of the core bridged 9‐aza‐[4.2.1]nonane skeleton via a Sc(OTf)3‐catalyzed intramolecular cross [3+2] cycloaddition (IMCC) followed by Krapcho decarboxylation and Barton reductive decarboxylation. The present work supplies a general and efficient strategy for synthesis of other bridged analogues.magnified image

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Enantioselective Formal Total Syntheses of Didehydrostemofoline and Isodidehydrostemofoline through a Catalytic Dipolar Cycloaddition Cascade

Cited by 14 publications

References 36 publications

Recent Advances in the Synthesis of Stemona Alkaloids

Recent Advances in the Synthesis of Stemona Alkaloids

Enantioselective total syntheses of (+)-stemofoline and three congeners based on a biogenetic hypothesis

Synthesis of (−)‐Pyrido[3,4‐b]homotropane (PHT) and (±)‐PHT via an Intramolecular Cross [3+2] Cycloaddition Strategy

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