Concise Stereoselective Routes to Advanced Intermediates Related to Natural and Unnatural Pinnaic Acid

Carson, Matthew W.; Kim, Guncheol; Hentemann, Martin F.; Trauner, Dirk

doi:10.1002/1521-3757(20011203)113:23<4582::aid-ange4582>3.0.co;2-g

Cited by 23 publications

(33 citation statements)

References 38 publications

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“…Formation of the C15AC16 double bond with Weinreb's phosphonate (28) (11) (Scheme 4 Inset) required oxidation of the C15 primary alcohol to the corresponding aldehyde. However, it is well known from published work in similar systems that protection of the proximal nitrogen is difficult because of its extremely hindered steric environment † (4,5,13,14). We decided to use a ␤-lactam group for simultaneous protection for the nitrogen atom and the C5 side chain during C13 side-chain elaboration (Scheme 4).…”

Section: Methodsmentioning

confidence: 73%

“…The structures of pinnaic and tauropinnaic acids were incompletely determined with NMR methods (2). Danishefsky's total synthesis of pinnaic acid (4,5) resolved the initial conjecture (2) regarding the relative configuration at C14 and revealed the configuration at C17 of pinnaic and tauropinnaic acids. Both compounds are now known to have the same relative configuration as the equivalent substructure of halichlorine.…”

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confidence: 99%

“…This activity may also give these compounds anti-inflammatory properties (2,(8)(9)(10). Many research groups have reported research directed toward synthesis of these alkaloids (4,5,(11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25)(26)(27)). Danishefsky's research group has reported syntheses of both halichlorine (13,14) and pinnaic acid (4,5).…”

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confidence: 99%

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Total synthesis of (±)-halichlorine, (±)-pinnaic acid, and (±)-tauropinnaic acid

Christie

Heathcock

2004

Proc. Natl. Acad. Sci. U.S.A.

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The related marine natural products halichlorine, pinnaic acid, and tauropinnaic acid have been synthesized. The described route provided access to all three compounds from a common, late-stage intermediate. The synthesis began with 1-pyrrolidino-1-cyclopentene from which an intermediate possessing the three contiguous stereocenters of the natural products was synthesized in just four steps. Olefin cross metathesis followed by a hydrogenation͞hydrogenolysis reaction stereoselectively formed the piperidine ring. Use of a ␤-lactam group provided internal protection for the highly congested nitrogen atom during side-chain elaboration. The ␤-lactam was subsequently reduced directly to an amino aldehyde, which after the HornerWadsworth-Emmons reaction was elaborated to pinnaic acid. The same amino aldehyde was also transformed into halichlorine after a thiol-mediated cyclization sequence to form the dehydroquinolizidine ring system.

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Section: Methodsmentioning

confidence: 73%

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confidence: 99%

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Total synthesis of (±)-halichlorine, (±)-pinnaic acid, and (±)-tauropinnaic acid

Christie

Heathcock

2004

Proc. Natl. Acad. Sci. U.S.A.

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“…Furthermore, the gross structure of 8 was elucidated by a detailed comparison of the EI-MS fragment peaks with the corresponding peaks of 9 . Synthetic studies of pinnaic acid ( vide infra ) unambiguously established that the relative stereochemistry of pinnaic acid is similar to that of 7 [31–33]. …”

Section: Resultsmentioning

confidence: 99%

“…The Danishefsky group has achieved the total synthesis of pinnaic acid [31,32] and halichlorine [17,18] in an asymmetric manner. Since pinnaic acid is a zwitterionic molecule, the NMR spectrum is quite sensitive to the measurement conditions.…”

Section: Resultsmentioning

confidence: 99%

Bioactive Alkaloids from the Sea: A Review

2004

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In our ongoing search for bioactive substances from marine organisms, novel alkaloids have been isolated. Pinnatoxins and pinnamine, potent shellfish poisons, were purified from the Okinawan bivalve Pinna muricata. Pinnatoxins activate Ca 2+ channels. Halichlorine was isolated from the marine spongeHalichondria okadai. This compound inhibits the induction of VCAM-1. Drugs that block VCAM-1 may be useful for treating coronary artery diseases, angina, and noncardiovascular inflammatory diseases. Pinnaic acids, which are cPLA 2 inhibitors, were also obtained from P. muricata. Interestingly, the structures of pinnaic acids are closely related to that of halichlorine. Norzoanthamine hydrochloride, isolated from the colonial zoanthid Zoanthus sp., suppresses decreases in bone weight and strength in ovariectomized mice, and could be a good candidate for an osteoporotic drug. Ircinamine, purified from the marine sponge Ircinia sp., has a reactive thioester. Aburatubolactams, inhibitors of superoxide anion generation, were isolated from Streptomyces sp. This article covers the bioactive marine alkaloids that have been recently isolated by this research group.

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DieB-Alkyl-Suzuki-Miyaura-Kreuzkupplung: Entwicklung, Untersuchungen zum Mechanismus und Anwendungen in der Naturstoffsynthese

2001

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Die Entwicklung neuer Reaktionen zur Erleichterung effizienter und kreativer Synthesen von Zielmolekülen jedweder Art übt eine anhaltende Faszination auf Chemiker aus. Ob eine neue Reaktion einen bedeutenden Beitrag leistet, wird mit der Zeit anhand der Akzeptanz unter möglichen Anwendern entschieden. Die B‐Alkyl‐Suzuki‐Miyaura‐Kreuzkupplung scheint eine solche bedeutende Reaktion zu sein. Seit ihrer Veröffentlichung durch Suzuki und Miyaura im Jahre 1986 hat sie sich wiederholt als attraktive Lösung für herausfordernde Syntheseprobleme erwiesen.

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Concise Stereoselective Routes to Advanced Intermediates Related to Natural and Unnatural Pinnaic Acid

Cited by 23 publications

References 38 publications

Total synthesis of (±)-halichlorine, (±)-pinnaic acid, and (±)-tauropinnaic acid

Total synthesis of (±)-halichlorine, (±)-pinnaic acid, and (±)-tauropinnaic acid

Bioactive Alkaloids from the Sea: A Review

DieB-Alkyl-Suzuki-Miyaura-Kreuzkupplung: Entwicklung, Untersuchungen zum Mechanismus und Anwendungen in der Naturstoffsynthese

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