Approaches to the synthesis of ingenol

Kim, Sanghee; Winkler, Jeffrey D.

doi:10.1039/cs9972600387

Cited by 63 publications

(34 citation statements)

References 32 publications

(48 reference statements)

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“…Brilliant use of olefin metathesis reactions in a complex setting was made by Wood and co‐workers in their recent total synthesis of ingenol ( 16 , Scheme ) 42. The parent member of a large class of ingenane diterpenes, ingenol ( 16 ) has captivated the attention of synthetic chemists for more than 20 years 43. The irresistible lure of this natural product is due partly to its promising biological activity,44 but also to its rather remarkable polycyclic, highly oxygenated molecular architecture, the most distinctive feature of which is the strained “inside–outside” ( trans ) intrabridgehead stereochemistry of the bicyclic BC‐ring system 45.…”

Section: The Alkene‐metathesis Reactionmentioning

confidence: 68%

Metathesis Reactions in Total Synthesis

2005

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With the exception of palladium-catalyzed cross-couplings, no other group of reactions has had such a profound impact on the formation of carbon-carbon bonds and the art of total synthesis in the last quarter of a century than the metathesis reactions of olefins, enynes, and alkynes. Herein, we highlight a number of selected examples of total syntheses in which such processes played a crucial role and which imparted to these endeavors certain elements of novelty, elegance, and efficiency. Judging from their short but impressive history, the influence of these reactions in chemical synthesis is destined to increase.

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Section: The Alkene‐metathesis Reactionmentioning

confidence: 68%

Metathesis Reactions in Total Synthesis

2005

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“…In 1997, Kim and Winkler surveyed the approaches that have been examined in various laboratories with the goal of the synthesis of ingenanes 129. The published approaches included inter‐ and intramolecular [6 + 4] cycloadditions of tropones to dienes, intramolecular [4 + 3] cycloadditions of cyclic oxyallyls to a tethered furan, Lewis‐acid‐catalysed aldol cyclization, photoinduced ring expansion/ring contraction, a ring contraction strategy based on the Ireland–Claisen rearrangement, and transformation of an out–out system to an in–out isomer by [1,5]‐hydrogen sigmatropic rearrangement and intramolecular dioxenone photocycloaddition and fragmentation.…”

Section: Ingenol 3‐angelate (Picato®)mentioning

confidence: 99%

Diterpenes from European Euphorbia Species Serving as Prototypes for Natural‐Product‐Based Drug Discovery

et al. 2012

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A nanotemplate surface that functions as a regular array of traps for molecules such as naphthalocyanine (see picture) is provided by a nanomesh of hexagonal BN on Rh(111), which has now been identified as a single, complete monolayer. The 2‐nm‐sized pores form at regions where the layer binds strongly to the underlying metal, while the regular network of mesh wires corresponds to regions where the layer is not bonded to the substrate.

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“…Ingenol mebutate (picato; Figure 1) was recently approved by the FDA as a first‐in‐class drug for the topical treatment of actinic keratosis, a precancerous skin condition 6. Consequently, some elegant synthetic strategies for the formation of bridged seven‐membered‐ring systems have been developed,1g,h, 2e including rearrangement,1d,f, 4f fragmentation,1c, 4e ring‐closing metathesis,1e and intramolecular cyclizations 2c,d. 3c However, so far no general reactions are available for the direct and efficient synthesis of bridged cycloheptane bicyclic systems.…”

Section: Methodsmentioning

confidence: 99%

Type II Intramolecular [5+2] Cycloaddition: Facile Synthesis of Highly Functionalized Bridged Ring Systems

et al. 2014

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A type II intramolecular oxidopyrylium-mediated [5+2] cycloaddition reaction allows the efficient and diastereoselective formation of various highly functionalized and synthetically challenging bridged seven-membered ring systems (such as bicyclo[4.4.1]undecane, bicyclo[4.3.1]decane, bicyclo[5.4.1]dodecane, and bicyclo[6.4.1]]tridecane). This simple, thermal, direct transformation has a broad substrate scope and is high yielding, with high functional-group tolerance and unique endo selectivity. The highly strained tricyclic cores of ingenol mebutate (picato) and cyclocitrinol are synthesized efficiently and diastereoselectively using this methodology.

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Approaches to the synthesis of ingenol

Cited by 63 publications

References 32 publications

Metathesis Reactions in Total Synthesis

Metathesis Reactions in Total Synthesis

Diterpenes from European Euphorbia Species Serving as Prototypes for Natural‐Product‐Based Drug Discovery

Type II Intramolecular [5+2] Cycloaddition: Facile Synthesis of Highly Functionalized Bridged Ring Systems

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