Synthesis of Oxa-Bridged Medium-Sized Carbocyclic Rings via Prins Cyclization

Wang, Minshou; Wang, Zheng; Chen, Wen; Yang, Xiaodong; Zhang, Hongbin

doi:10.1021/acs.orglett.9b00491

Cited by 18 publications

(28 citation statements)

References 80 publications

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“…Retrosynthetic analysis. As part of our ongoing program in seeking flexible and divergent synthetic strategies toward bioactive natural products and its analogues [57][58][59][60][61] , we recently disclosed a Lewis acid-mediated intramolecular Prins reaction of dioxinones to construct medium-sized carbocycles bearing oxabridged bicyclic structural units 62 . We envisioned that the Mannich-type-cyclization version of our previous protocol might lead to the highly functional 9-azabicyclo[3.3.1]nonane ring system (16, Fig.…”

Section: Resultsmentioning

confidence: 99%

Structure units oriented approach towards collective synthesis of sarpagine-ajmaline-koumine type alkaloids

Chen

et al. 2022

Nat Commun

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Sarpagine-Ajmaline-Koumine type monoterpenoid indole alkaloids represent a fascinating class of natural products with polycyclic and cage-like structures, interesting biological activities, and related biosynthetic origins. Herein we report a unified approach towards the asymmetric synthesis of these three types of alkaloids, leading to a collective synthesis of 14 natural alkaloids. Among them, akuammidine, 19-Z-akuammidine, vincamedine, vincarine, quebrachidine, vincamajine, alstiphylianine J, and dihydrokoumine are accomplished for the first time. Features of our synthesis are a new Mannich-type cyclization to construct the key indole-fused azabicyclo[3.3.1]nonane common intermediate, a SmI2 mediated coupling to fuse the aza-bridged E-ring, stereoselective olefinations to install either the 19-E or 19-Z terminal alkenes presented in the natural alkaloids, and an efficient iodo-induced cyclization to establish the two vicinal all-carbon quaternary centers in the Koumine-type alkaloids.

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Section: Resultsmentioning

confidence: 99%

Structure units oriented approach towards collective synthesis of sarpagine-ajmaline-koumine type alkaloids

Chen

et al. 2022

Nat Commun

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“…Because of their fascinating structures and biological importance, natural products containing eight-membered rings have attracted considerable attention from the synthetic community. Nowadays, numerous methodologies have been developed to construct eight-membered ring systems, some of which were reported very recently, − and many of which have also been applied to total synthesis of cyclooctanoids. Nevertheless, more practical, flexible, and efficient strategies to synthesize eight-membered rings are still required.…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in the Total Synthesis of Natural Products Containing Eight-Membered Carbocycles (2009–2019)

Han

et al. 2020

Chem. Rev.

137

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Natural products containing eight-membered carbocycles constitute a class of structurally intriguing and biologically important molecules such as the famous diterpenes taxol and vinigrol. Such natural products are being increasingly investigated because of their fascinating architectural features and potent medicinal properties. However, synthesis of natural products with cyclooctane moieties has proved to be highly challenging. This review highlights the recently completed total syntheses of natural products with eight-membered carbocycles with a focus on strategic considerations. A collection of 27 representative studies from the literature covering the decade from 2009 to 2019 is described in chronological order with relevant studies grouped together, including syntheses of the same natural product by different research groups using different strategies. Finally, a summary and outlook including a discussion of the major features of each strategy used in the syntheses are presented. This review illustrates the diversity and creativity in the elegant synthetic designs of eight-membered carbocycles. We hope this review will provide timely illumination and beneficial guidance for future synthetic efforts for organic chemists who are interested in this area.

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“…将化合物 13 经臭氧化反应和路易斯诱导的 Prins 环化反应后, 成功地实现了五元并七元氧桥环的构建, 得到了化合物 14 (Scheme 2). 化合物 14 经过单晶 X 射线的测试, 证实了其 [5,7]并环结构及其立体化学关系 [17] . 该化合物的主体环系结构由五元环并七元氧桥环组成, 其中五元环和七元环结构呈反式稠合关系, 乙氧酰基与氧桥呈反式关系.…”

Section: 结果与讨论unclassified

“…该化合物的主体环系结构由五元环并七元氧桥环组成, 其中五元环和七元环结构呈反式稠合关系, 乙氧酰基与氧桥呈反式关系. 13 C NMR (100 MHz, CDCl 3 ) δ: 174.84, 168.97, 161.11, 134.29, 118.20, 106.70, 96.23, 82.48, 60.96, 60.79, 41.09, 36.77, 35.54, 30.18, 25.26, 25.04, 18.84, 14.26 [17] 合成化合物 14.…”

Section: 结果与讨论unclassified