Synthetic studies on rabdosia diterpene lactones II: The synthesis of 15-desoxyeffusin

Kenny, Martin J.; Mander, Lewis N.; SETHI, S. P.

doi:10.1016/s0040-4039(00)83919-2

Cited by 27 publications

(10 citation statements)

References 15 publications

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“…Total synthesis of the first 6,7‐seco‐ ent ‐kauranoid related to trichorabdal A ( 2 ) can be traced back to as early as 1972, when Fujita and co‐workers synthetically achieved enmein ( 6 ), which was a landmark in the field ,. After that, no new syntheses were documented until Mander and co‐workers disclosed a total synthesis of desoxyeffusin in 1986 and a semisynthesis of longirabdolactone ( 5 ) from gibberellic acid in 2003 . In recent years, the interest in 6,7‐seco‐ ent ‐kauranoids surged and resulted in several elegant synthetic achievements.…”

Section: Figurementioning

confidence: 99%

Total Syntheses of Trichorabdal A and Maoecrystal Z

Chen

Zhang

et al. 2018

Chemistry A European J

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This work reports the total syntheses of Isodon diterpenes trichorabdal A and maoecrystal Z via a common bicyclo[3.2.1]octane intermediate, which chemically bridges the two distinct structures through a retro-aldol/aldol reaction cascade. Other synthetic features include an efficient cross-ring radical cyclization for rapid construction of an all carbon quaternary center commonly seen in Isodon diterpenoids, a challenging Ueno-Stork cyclization on to a sensitive 1,6-enone system, as well as a serial of chemoselective functional group manipulations in complex chemical environments.

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Section: Figurementioning

confidence: 99%

Total Syntheses of Trichorabdal A and Maoecrystal Z

Chen

Zhang

et al. 2018

Chemistry A European J

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“…Mander 等 [33] 以已知的合成中间体 98 出发, 通过合成 102 再发生 C(6)-C(7)键的切断实现对(±)-15-desoxyeffusin 的合成. 在这一策略中, 作者先立体选择性的构建 B/C/D 环体系, 通过 C-10 位的手性经分子内 Micheal 加成反应和分子内卤原子取代反应分别控制 C-5 位和 C-4 位的手性(Scheme 17).…”

Section: Mander 组对(±)-15-desoxyeffusin 的合成unclassified

Advanced in the Synthesis of Kaurane Diterpenoids

Du¹,

Lei²

2015

Chin. J. Org. Chem.

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“…In 1986, Mander and co-workers reported the synthesis of 15-deoxy effusin ( 9 ) in 33 steps from 3,5-dimethoxybenzoic acid ( 7 ) (Scheme ). In 2003, the same group reported a 29-step preparation of longirabdolactone ( 5 ) from gibberellic acid ( 10 ) . Here, we report the first asymmetric total syntheses of longirabdiol ( 4 ), longirabdolactone ( 5 ), and effusin ( 6 ) via three free-radical-based reactions …”

Section: Introductionmentioning

confidence: 99%

Tandem Decarboxylative Cyclization/Alkenylation Strategy for Total Syntheses of (+)-Longirabdiol, (−)-Longirabdolactone, and (−)-Effusin

Zhang

Zhuo

et al. 2019

J. Am. Chem. Soc.

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Structurally complex and bioactive ent-kaurane diterpenoids have well-characterized biological functions and have drawn widespread attention from chemists for many decades. However, construction of highly oxidized forms of such diterpenoids still presents considerable challenges to synthetic chemists. Herein, we report the first total syntheses of C19 oxygenated spiro-lactone ent-kauranoids, including longirabdiol, longirabdolactone, and effusin. A concise synthesis of the common intermediate used for all three syntheses was enabled via three free-radical-based reactions: (1) a newly devised tandem decarboxylative cyclization/alkenylation sequence that forges the cis-19, 6-lactone concomitantly with vicinal alkenylation, (2) a Ni-catalyzed decarboxylative Giese reaction that constructs C10 quaternary center stereoselectively, and (3) a vinyl radical cyclization that generates a rigid bicyclo[3.2.1]octane. A series of late-stage oxidations from the common intermediate then provided each of the natural products in turn. Further biological evaluation of these synthetic natural products reveals broad anticancer activities.

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Synthetic studies on rabdosia diterpene lactones II: The synthesis of 15-desoxyeffusin

Cited by 27 publications

References 15 publications

Total Syntheses of Trichorabdal A and Maoecrystal Z

Total Syntheses of Trichorabdal A and Maoecrystal Z

Advanced in the Synthesis of Kaurane Diterpenoids

Tandem Decarboxylative Cyclization/Alkenylation Strategy for Total Syntheses of (+)-Longirabdiol, (−)-Longirabdolactone, and (−)-Effusin

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