Synthesis of (4R,15R,16R,21S)- and (4R,15S,16S,21S)-rollicosin, squamostolide, and their inhibitory action with bovine heart mitochondrial complex I

Makabe, Hidefumi; Kimura, Yoshihide; Higuchi, Masaharu; Konno, Hiroyuki; Murai, Masatoshi; Miyoshi, Hideto

doi:10.1016/j.bmc.2005.12.015

Cited by 15 publications

(8 citation statements)

References 28 publications

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“…Miyoshi's group used stabilized lithium-α-thiolactones in the key steps for the asymmetric synthesis of rollicosin and squamostolide (Scheme 8.4) [26]. In this sequence, the SPh group is used for stabilizing the α-lithiated γ-lactone anion and as precursor of the sulfinyl group (by meta-chloroperoxybenzoic acid (m-CPBA) oxidation) that suffers the syn-pyrolytic elimination, affording the butenolide ring.…”

Section: Thioethersmentioning

confidence: 99%

Sulfur‐Bearing Lithium Compounds in Modern Synthesis

Ruano

Parra

Alemán

2014

Lithium Compounds in Organic Synthesis

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Sulfur functions have been widely used for the stabilization of lithium carbanions. Their different oxidation states determine a variety of mechanisms for such stabilization, mainly related with their electronic effects (−I and −M) and associative abilities and also with the relative position of sulfur with respect to the C-Li bond. As additional interest, the sulfur of some of these functions is a stable stereogenic center, and their interactions with prochiral lithium carbanions are able to control the stereochemical course of their reactions with electrophiles, which can be successfully used in asymmetric synthesis. Finally, the chemical versatility of the sulfur functions and their easy elimination under diverse conditions confer to the sulfur-stabilized lithium carbanions a very important role in modern synthetic chemistry. In this chapter, we have organized the information attending to the relative position of the carbanionic center with respect to the sulfur function (α-, β-, and γ-lithiation, see Figure 8.1). Each item has been subdivided according to the nature of the sulfur function stabilizing the carbanion. In this sense, sulfoxides, sulfones, and sulfoximines are the three main functions stabilizing any type of lithium-carbanions, but the thioethers have also been described as stabilizing in αand β-lithiation processes. The fragment connecting S and Li is always formed by carbon atoms, but N is present in some cases of γ-lithiation.This chapter covers the literature of the last 10-12 years concerning the preparation and main synthetic applications of the lithium carbanions stabilized by sulfur functions. In most of the cases, the information that appeared in this century helps understand the role of the sulfur functions in the stabilization of the lithium carbanions, and therefore we have only mentioned, as introduction, the seminal references in the field. However, in those cases where there are few references in the last decade and most of the information has been reported before 2000, we have included and briefly commented on the most significant contributions to be able to understand the interest of such stabilizing functions. During the last decade have appeared excellent revisions concerning the reactivity and structure of lithium carbanions [1], the use of different sulfur functions in asymmetric synthesis [2], as Lithium Compounds in Organic Synthesis: From Fundamentals to Applications, First Edition. Edited by Renzo Luisi and Vito Capriati.

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Section: Thioethersmentioning

confidence: 99%

Sulfur‐Bearing Lithium Compounds in Modern Synthesis

Ruano

Parra

Alemán

2014

Lithium Compounds in Organic Synthesis

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“…(4 R ,15 S ,16 S ,21 S )-Rollicosin ( 610b ) was also obtained starting from 620b using the same procedure as that employed for 610a . In 2006, the full details of this total synthesis were reported [ 190 ].…”

Section: Reviewmentioning

confidence: 99%

“…Squamostolide ( 622 ), which was isolated from Annona squamosa by Wei’s group [ 191 ], showed a remarkably weak inhibitory activity compared to ordinary acetogenins such as bullatacin [ 191 ]. In 2006, Makabe’s group reported the total synthesis of squamostolide ( Scheme 101 ) [ 190 ]. The lactone 622 was obtained by alkylation of the enolate prepared from 15 using NaHMDS with diiodide 623 .…”

Section: Reviewmentioning

confidence: 99%

Recent progress on the total synthesis of acetogenins from Annonaceae

Li¹,

Shi²,

Tang³

et al. 2008

Beilstein J. Org. Chem.

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An overview of recent progress on the total synthesis of acetogenins from Annonaceae during the past 12 years is provided. These include mono-tetrahydrofurans, adjacent bis-tetrahydrofurans, nonadjacent bis-tetrahydrofurans, tri-tetrahydrofurans, adjacent tetrahydrofuran-tetrahydropyrans, nonadjacent tetrahydrofuran-tetrahydropyrans, mono-tetrahydropyrans, and acetogenins containing only γ-lactone. This review emphasizes only the first total synthesis of molecules of contemporary interest and syntheses that have helped to correct structures. In addition, some significant results on the novel synthesis and structure-activity relationship studies of annonaceous acetogenins are also introduced.

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“…For instance, the desymmetrization of diols [3] [4] [5] [6] [7], dicarbonyls [8] [9] [10] [11] [12], diamines [13], and alkenes [14] [15] [16] has been successfully applied to the synthesis of natural products such as (-)-spongidepsin [7] and merrilactone A [9] [10]. In particular, the monoprotection of diols with the tetrahydropyranyl (THP) group has been widely used in the synthesis of bioactive compounds [17] [18] [19] [20]. However, these transformations usually result in the concomitant generation of unprotected and/or diprotected compounds in a statistical ratio.…”

Section: Introductionmentioning

confidence: 99%

Selective Monoprotection of Symmetrical Diols in a Flow Reactor

Masui¹,

Takizawa²,

Sakai³

et al. 2018

IJOC

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Desymmetrization reactions provide a powerful approach for the construction of complex molecules. Various methods have been developed for the selective monoprotection of symmetrical diols; however, their application to large-scale operations is limited. In this study, the monotetrahydropyranylation of symmetrical diols in a flow reactor has been developed, whereby the length of the flow reactor tube and the amount of acid were optimized. A higher selectivity for the monoprotected derivative was observed when the reaction was performed in a flow reactor compared with that observed in a conventional batch experiment. The efficient flow method developed herein can be applied to large-scale synthesis by numbering up the flow reactor without affecting the selectivity and yield. Since monoprotection can be achieved without using a large excess of diol, our developed flow method is effective when expensive diol must be used.

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Synthesis of (4R,15R,16R,21S)- and (4R,15S,16S,21S)-rollicosin, squamostolide, and their inhibitory action with bovine heart mitochondrial complex I

Cited by 15 publications

References 28 publications

Sulfur‐Bearing Lithium Compounds in Modern Synthesis

Sulfur‐Bearing Lithium Compounds in Modern Synthesis

Recent progress on the total synthesis of acetogenins from Annonaceae

Selective Monoprotection of Symmetrical Diols in a Flow Reactor

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