Lipase‐Promoted Access to Phenolic Herbertane‐Type Sesquiterpenes: (+)‐1,14‐Herbertenediol, (−)‐α‐Herbertenol, (−)‐Herbertenediol and Their Enantiomers

Acherar, Samir; Audran, Gérard; Fotiadu, Fréderic; Monti, H.

doi:10.1002/ejoc.200400395

Cited by 12 publications

(3 citation statements)

References 41 publications

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“…This large group of natural compounds possesses chemical frameworks very different from each other, and the features of the developed enzymatic processes are strictly dependent on the structures of the substrates involved in the resolution step. The most representative secondary alcohols are cyclohexane or cyclopentane derivatives [76][77][78][79][80][81][82][83][84][85][86][87][88][89], even if cycloheptane [90] and cycloundecane [91] derivatives have been resolved by using lipases (Figure 16). Concerning cyclohexane secondary alcohols, the chiral building blocks 93-97 were obtained by acetylation or hydrolysis of the corresponding alcohols (93, 95, and 96), diol (94), and butyrate (97) derivatives.…”

Section: Secondary Alcoholsmentioning

confidence: 99%

“…Acetate 102 [82] was specially prepared and used in the multistep synthesis affording the optically active azulene derivative 109, useful for terpenoid synthesis. The ester 103 [83] has been employed for the preparation of the herbetane sesquiterpenes (−)-α-herbetenol (110), (−)-herbetenediol, and (+)-1,14-herbetenediol. A very similar chiral building block [84] was used for the synthesis of the cuparene sesquiterpene β-cuparenone [85], whereas the alcohol 104 [86] was employed in the synthesis of the monoterpene (−)-β-necrodol (111).…”

Section: Secondary Alcoholsmentioning

confidence: 99%

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Stereoselective Synthesis of Terpenoids through Lipase-Mediated Resolution Approaches

Serra¹,

Simeis²

2020

Catalysts

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This review article focuses on the scientific developments concerning the lipase-mediated synthesis of terpenoids that have been reported in the literature during the last twenty years. More specifically, this review describes in depth the resolution approaches that allow the preparation of the chiral building blocks used for the stereoselective synthesis of bioactive terpenoids. The synthetic methods that have given new and innovative perspectives from a scientific standpoint, and the preparative approaches that possess industrial importance, are described thoroughly.

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Section: Secondary Alcoholsmentioning

confidence: 99%

Section: Secondary Alcoholsmentioning

confidence: 99%

Stereoselective Synthesis of Terpenoids through Lipase-Mediated Resolution Approaches

Serra¹,

Simeis²

2020

Catalysts

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“…104 Syntheses of (±)-1,13herbertenediol and other C-13 oxidized cuparene and herbertane sesquiterpenes have been reported. 105,106 Enantioselective syntheses of (−)-a-herbertenol, 107 (+)-1,14-herbertenediol, and a formal synthesis of (−)-a-herbertenol and (−)herbertenediol 108 have been described, whilst a racemic synthesis of herbertenolide has appeared. 109 The gymnomitrane derivative 74 has been isolated from an extract of the liverwort Bazzania trilobata.…”

Section: Fumagillanementioning

confidence: 99%

Natural sesquiterpenoids

Fraga

2005

Nat. Prod. Rep.

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The Barton‐McCombie Reaction

2012

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Deoxygenations of alcohols, i.e., processes that replace a hydroxyl group with hydrogen at a saturated carbon, find applications in both total synthesis and the systematic modifications of natural products. They may also be employed to introduce deuterium or tritium in a site‐specific manner. Reductive methods that involve ionic or highly polarized reagents or intermediates can be limited in their applicability: for example, competing reaction pathways including cationic rearrangements and anionic eliminations may be encountered in sterically hindered systems with substrates bearing heteroatoms close to the center undergoing reduction. As evidenced by developments over the last few decades, methods that involve the generation and direct quenching via hydrogen atom abstraction of the derived, carbon‐centered radical typically show the greatest tolerance for the presence of other functional groups and for variations in both the steric acid and the electronic environment in the vicinity of the center undergoing deoxygenation. Derivatization of the hydroxyl is a prerequisite, the determinant factors for efficient formation of the deoxygenated product lies in the ability of the combination of the substrate and reagents to induce homolysis of the C‐O bond coupled with the induction of homolysis to rapidly reduce a free radical by hydrogen donation, thereby propagating an efficient chain process. A high‐yielding way to realize this sequence was first described by Barton McCombie using the free‐radical chain reaction of O ‐thioacyl derivatives of secondary alcohols with tri‐ n ‐butylstannane. This chapter provides a detailed description and comparison of the combinations of substrates and reagents that will bring about these processes and provides a summary and evaluation of alternative deoxygenation methods. Mechanistic and stereochemical issues set out the scope and limitations of these processes with respect to both the thioacylation and reduction steps and exemplify some applications to both total synthesis and the modification of natural products.

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Lipase‐Promoted Access to Phenolic Herbertane‐Type Sesquiterpenes: (+)‐1,14‐Herbertenediol, (−)‐α‐Herbertenol, (−)‐Herbertenediol and Their Enantiomers

Cited by 12 publications

References 41 publications

Stereoselective Synthesis of Terpenoids through Lipase-Mediated Resolution Approaches

Stereoselective Synthesis of Terpenoids through Lipase-Mediated Resolution Approaches

Natural sesquiterpenoids

The Barton‐McCombie Reaction

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