Synthetic strategies toward hetidine and hetisine-type diterpenoid alkaloids

Hamlin, Amy M.; Kisunzu, Jessica K.; Sarpong, Richmond

doi:10.1039/c3ob42541j

Cited by 53 publications

(13 citation statements)

References 26 publications

(30 reference statements)

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“…Natural products containing complex three-dimensional structures represent challenging synthetic targets, and compounds of this type have consequently received considerable interest from research groups all over the world 1 – 3 . Notably, cage-shaped natural products have been reported to show several interesting biological activities, and numerous polycyclic terpene 4 – 7 and alkaloid 8 targets of this type have inspired synthetic chemists to develop innovative new strategies to access these compounds. Non-cage-shaped natural products that are capable of being converted to cage-shaped materials also exhibit an interesting range of biological activities, as exemplified by avenaol 9 , shagene A 10 , erythrolide A 11 and arisanlactone C 12 (Fig.…”

Section: Introductionmentioning

confidence: 99%

Total synthesis of avenaol

et al. 2017

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Avenaol, isolated from the allelopathic plant black oat, was the first C20 germination stimulant related to strigolactones. Structurally, it consisted of a bicyclo[4.1.0]heptanone skeleton containing a cyclopropane ring bearing three main chains projecting in the same direction (i.e. all-cis-substituted cyclopropane). Herein, we report the total synthesis of avenaol using a robust strategy involving the formation of an all-cis-substituted cyclopropane via an alkylidenecyclopropane. The key factors in the success of this total synthesis include the Rh-catalysed intramolecular cyclopropanation of an allene, an Ir-catalysed stereoselective double-bond isomerisation, and the differentiation of two hydroxymethyl groups via the regioselective formation and oxidation of a tetrahydropyran based on the reactivity of a cyclopropyl group. This strategy effectively avoids the undesired ring opening of the cyclopropane ring and the formation of a caged structure. Furthermore, this study confirms the proposed structure of avenaol, including its unique all-cis-substituted cyclopropane moiety.

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Section: Introductionmentioning

confidence: 99%

Total synthesis of avenaol

et al. 2017

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“…[14] Sarpong and co-workers contributed ac omprehensive review on synthetic strategies towards the hetidine-and hetisine-typed iterpenoid alkaloids in 2014. [15] The past five years have witnessed remarkable achievements in the syntheses of diterpenoid alkaloids, including two new approaches to the atisine alkaloids (1-3), [16,17] two strategies towards the hetidine scaffold, [17,18] the first enantioselective synthesis of denudatine alkaloid (À)-lepenine (8), [19] and the first synthesis of al appaconitine-type alkaloid (AE)-neofinaconitine (12). [20] The purpose of this review is to cover the completed total syntheses or syntheses of the entire skeletons of diterpenoid alkaloids reported since 2010, showcasing the creative solutions through the use of moderno rganic methods.…”

Section: Introductionmentioning

confidence: 99%

Ongoing Pursuit of Diterpenoid Alkaloids: A Synthetic View

Liu

Qin

2015

Asian J Org Chem

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The incorporation of nitrogen atoms into policyclic diterpenes has led to one of the most fascinatingg roup of natural products with cage-like structures:d iterpenoid alkaloids. Their singular architectural features and significant bioactivitiesm ade them highly pursued targets amongst the synthetic community over decades. At otal of seven types of diterpenoid alkaloid molecules have been synthesized thus far,a nd the research in this area experiencedanew climax in the past five years. With ab rief overview and summary of the historic achievements, this Focus Review particularly covers the recent,post-2010 advances in the field of diterpenoid alkaloid synthesis, highlighting the utilizationofinnovative synthetic methods and strategies. Despite numerous achievements, there are stillanumber of such alkaloids with differenta nd uniques tructural types waiting to be accomplished, implying that the pursuit is far from ending.

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“…Early important contributions to the syntheses of the diterpenoid alkaloids (including a synthesis of talatisamine, 3 , and atisine, 9 ) were made by Wiesner and co-workers, 7 and recently, syntheses of nominine ( 12 , by the groups of Gin 8 and Muratake and Natsume 9 ), neofinaconitine ( 2 , by Gin and co-workers), 10 and lepenine ( 4 , by Fukuyama, Yokoshima, and co-workers) 11 have appeared. 12 …”

Section: Introductionmentioning

confidence: 99%

Studies on C₂₀-Diterpenoid Alkaloids: Synthesis of the Hetidine Framework and Its Application to the Synthesis of Dihydronavirine and the Atisine Skeleton

et al. 2014

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The full details of a synthesis of the hetidine framework of the C20-diterpenoid alkaloids and its conversion to the atisine core structure are reported. The application of the hetidine framework to the synthesis of dihydronavirine, which is the formal reduction product of the natural product navirine, is also described. Key to the success of these studies is the use of a Ga(III)-catalyzed cycloisomerization reaction of alkynylindenes to prepare a [6–7–6] framework that was advanced to the hetidine skeleton. Furthermore, a Michael/aldol sequence was developed for the construction of the bicyclo[2.2.2] framework that is characteristic of the hetidines and atisines.

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Synthetic strategies toward hetidine and hetisine-type diterpenoid alkaloids

Cited by 53 publications

References 26 publications

Total synthesis of avenaol

Total synthesis of avenaol

Ongoing Pursuit of Diterpenoid Alkaloids: A Synthetic View

Studies on C₂₀-Diterpenoid Alkaloids: Synthesis of the Hetidine Framework and Its Application to the Synthesis of Dihydronavirine and the Atisine Skeleton

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Synthetic strategies toward hetidine and hetisine-type diterpenoid alkaloids

Cited by 53 publications

References 26 publications

Total synthesis of avenaol

Total synthesis of avenaol

Ongoing Pursuit of Diterpenoid Alkaloids: A Synthetic View

Studies on C20-Diterpenoid Alkaloids: Synthesis of the Hetidine Framework and Its Application to the Synthesis of Dihydronavirine and the Atisine Skeleton

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Studies on C₂₀-Diterpenoid Alkaloids: Synthesis of the Hetidine Framework and Its Application to the Synthesis of Dihydronavirine and the Atisine Skeleton