The total synthesis of (+)-ryanodol. Part IV. Preparation of (+)-ryanodol from (+)-anhydroryanodol

Deslongchamps, Pierre; Bélanger, André; Berney, Daniel; Borschberg, Hans‐Jürg; Brousseau, Robert; Doutheau, Alain; Durand, Robert; Katayama, Hajime; Lapalme, Richard; Leturc, D. M.; Liao, Chun‐Chen; MacLachlan, Frederick N.; Maffrand, Jean‐Pierre; Marazza, Fabrizio; Martino, Robert; Moreau, Claude; Ruest, Luc; Saint-Laurent, L.; Saintonge, Roger; Soucy, Pierre

doi:10.1139/v90-024

Cited by 33 publications

(16 citation statements)

References 4 publications

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“…18−22 Deslongchamps’s synthesis was guided by the discovery that (+)-anhydroryanodol ( 5 ) could be converted to 4 in two steps. 18 Deslongchamps, Ruest, and co-workers, 23 as well as an independent team lead by Casida, 24 subsequently went on to prepare a number of semisynthetic derivatives of 1 and 4 for use in pharmacological studies.…”

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confidence: 99%

Chemical Synthesis of (+)-Ryanodine and (+)-20-Deoxyspiganthine

Han

Virgil

et al. 2017

ACS Cent. Sci.

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(+)-Ryanodine is a natural product modulator of ryanodine receptors, important intracellular calcium ion channels that play a critical role in signal transduction leading to muscle movement and synaptic transmission. Chemical derivatization of (+)-ryanodine has demonstrated that certain peripheral structural modifications can alter its pharmacology, and that the pyrrole-2-carboxylate ester is critical for high affinity binding to ryanodine receptors. However, the structural variation of available ryanodine analogues has been limited by the challenge of site-specific functionalization of semisynthetic intermediates, such as (+)-ryanodol. Here we report a synthetic strategy that provides access to (+)-ryanodine and the related natural product (+)-20-deoxyspiganthine in 18 and 19 steps, respectively. A key feature of this strategy is the reductive cyclization of an epoxide intermediate that possesses the critical pyrrole-2-carboxylate ester. This approach allows for the direct introduction of this ester in the final stage of the synthesis and provides a framework for the synthesis of previously inaccessible synthetic ryanoids.

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confidence: 99%

Chemical Synthesis of (+)-Ryanodine and (+)-20-Deoxyspiganthine

Han

Virgil

et al. 2017

ACS Cent. Sci.

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“…222,223 As such, 178 and its derivatives represent both potent biochemical tools as well as potential medicinal and former agrochemical agents. 224–226 Three syntheses of ryanodol ( 177 ) have been reported by the groups of Deslongchamps (1979), 227–231 Inoue (2014), 232 and very recently Reisman (2016). 233 The Deslongchamps route to 177 was a landmark achievement in 20 th century terpene synthesis.…”

Section: Syntheses From the 21st Centurymentioning

confidence: 99%

Navigating the Chiral Pool in the Total Synthesis of Complex Terpene Natural Products

et al. 2017

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The pool of abundant chiral terpene building blocks (i.e. “chiral pool terpenes”) has long served as a starting point for the chemical synthesis of complex natural products, including many terpenes themselves. As inexpensive and versatile starting materials, such compounds continue to influence modern synthetic chemistry. This review highlights 21st century terpene total syntheses which themselves use small, terpene-derived materials as building blocks. An outlook to the future of research in this area is highlighted as well.

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“…Historically,o nly one successful synthesis of ryanodol was reported by Deslongchamps and co-workers in the last century. [40] In recent years, the Inoue,R eisman andM icalizio groups have successively made leaps in this field relying on their breathtaking inspirations on designing the synthetic strategies.…”

Section: Ryanodane Diterpenoidsmentioning

confidence: 99%

The Total Synthesis of Diquinane‐Containing Natural Products

Zhang

She

2021

Chemistry A European J

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Diquinane or bicyclo[3.3.0]octane is a conspicuous structural unit existing in the carbo‐frameworks of a wide range of natural products such as alkaloids and terpenoids. These diquinane‐containing molecules not merely exhibit intriguing architectures, but also showcase a broad spectrum of significant bioactivities, which draw widespread attention from the global synthetic community. During the past decade, with an aim to accomplish the total syntheses of such specified cornucopias of natural products, a variety of elegant strategies for construction of the diquinane ring system have been disclosed. In this Minireview, the achievements on this subject in the timeline from 2010 to June 2020 are demonstrated and it is discussed how the diquinane unit is strategically forged in the context of the specific target structure. In addition, impacts of the selected works to the field of natural product total synthesis is highlighted and the particular outlook of diquinane‐containing natural product synthesis is provided.

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The total synthesis of (+)-ryanodol. Part IV. Preparation of (+)-ryanodol from (+)-anhydroryanodol

Abstract: This paper reports the transformation of (+)-anhydroryanodol (6) to (+)-ryanodol (7) by reductive cyclization of lactone epoxide derivatives 9 and 20 (Scheme 4). Keywords: anhydroryanodol, ryanodol, diterpene, synthesis, reductive cyclization.

Cited by 33 publications

References 4 publications

Chemical Synthesis of (+)-Ryanodine and (+)-20-Deoxyspiganthine

Chemical Synthesis of (+)-Ryanodine and (+)-20-Deoxyspiganthine

Navigating the Chiral Pool in the Total Synthesis of Complex Terpene Natural Products

The Total Synthesis of Diquinane‐Containing Natural Products

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