The first catalytic asymmetric total synthesis of ent-hyperforin

Shimizu, Y.; Shi, Shiliang; Usuda, Hiroyuki; Kanai, Motomu; Shibasaki, Masakatsu

doi:10.1016/j.tet.2010.05.086

Cited by 41 publications

(15 citation statements)

References 46 publications

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“…The vinylogous Pummerer reaction has also found application in several natural product syntheses. In their route toward hyperforin, reported in 2010, Kanai, Shibasaki, and co-workers turned to a vinylogous Pummerer reaction to install a hydroxyl group in the γ-position, forming 92 (Scheme c) . In the model studies, the ratio of classic and vinylogous Pummerer products was found to be highly dependent on the base, with bulky pyridines such as 2,6-di- t -butylpyridine, giving the best results with yields between 70 and 80% for the vinylogous product (the real substrate yielded 65% of the desired product with an inconsequential dr > 33:1).…”

Section: Sulfoxidesmentioning

confidence: 99%

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

et al. 2019

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Organosulfur compounds have long played a vital role in organic chemistry and in the development of novel chemical structures and architectures. Prominent among these organosulfur compounds are those involving a sulfur(IV) center, which have been the subject of countless investigations over more than a hundred years. In addition to a long list of textbook sulfur-based reactions, there has been a sustained interest in the chemistry of organosulfur(IV) compounds in recent years. Of particular interest within organosulfur chemistry is the ease with which the synthetic chemist can effect a wide range of transformations through either bond formation or bond cleavage at sulfur. This review aims to cover the developments of the past decade in the chemistry of organic sulfur(IV) molecules and provide insight into both the wide range of reactions which critically rely on this versatile element and the diverse scaffolds that can thereby be synthesized.

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Section: Sulfoxidesmentioning

confidence: 99%

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

et al. 2019

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“…In early 2010 a catalytic asymmetric total synthesis of (−)-hyperforin was published by Shibasaki and coworkers [42]. Notably, this is the first catalytic asymmetric synthesis of any PPAP, since the previously reported asymmetric synthesis of clusianone involved a late-stage kinetic resolution (Section 12.2.4.4) [50].…”

Section: Total Synthesis Of (−)-Hyperforinmentioning

confidence: 97%

Polyprenylated Phloroglucinols and Xanthones

Theodorakis

2011

Biomimetic Organic Synthesis

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“…Finally, cross-metathesis to introduce the prenyl group at C-3 and methanolysis of the acetate under basic conditions completed the total synthesis of ent -hyperforin ( 422 ), the antipode of the naturally occurring substance, as confirmed by optical rotation measurements. The authors claim that these basic methods are also applicable to the asymmetric synthesis of other PPAPs and analogues of hyperforin. ,, …”

Section: Synthetic Chemistry Of Ppapsmentioning

confidence: 99%

Research Progress of Polycyclic Polyprenylated Acylphloroglucinols

2018

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Polycyclic polyprenylated acylphloroglucinols (PPAPs) are a class of hybrid natural products sharing the mevalonate/methylerythritol phosphate and polyketide biosynthetic pathways and showing considerable structure and bioactivity diversity. This review discusses the progress of research into the chemistry and biological activity of 421 natural PPAPs in the past 11 years as well as in-depth studies of biological activities and total synthesis of some PPAPs isolated before 2006. We created an online database of all PPAPs known to date at http://www.chem.uky.edu/research/grossman/PPAPs . Two subclasses of biosynthetically related metabolites, spirocyclic PPAPs with octahydrospiro[cyclohexan-1,5'-indene]-2,4,6-trione core and complicated PPAPs produced by intramolecular [4 + 2] cycloadditions of MPAPs, are brought into the PPAP family. Some PPAPs' relative or absolute configurations are reassigned or critically discussed, and the confusing trivial names in PPAPs investigations are clarified. Pharmacologic studies have revealed a new molecular mechanism whereby hyperforin and its derivatives regulate neurotransmitter levels by activating TRPC6 as well as the antitumor mechanism of garcinol and its analogues. The antineoplastic potential of some type B PPAPs such as oblongifolin C and guttiferone K has increased significantly. As a result of the recent appearances of innovative synthetic methods and strategies, the total syntheses of 22 natural PPAPs including hyperforin, garcinol, and plukenetione A have been accomplished.

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The first catalytic asymmetric total synthesis of ent-hyperforin

Cited by 41 publications

References 46 publications

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

Polyprenylated Phloroglucinols and Xanthones

Research Progress of Polycyclic Polyprenylated Acylphloroglucinols

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