Recent Developments in the Synthesis of Prostaglandins and Analogues

Das, Saibal; Chandrasekhar, Srivari; Yadav, J. S.; Grée, René

doi:10.1021/cr068365a

Cited by 250 publications

(103 citation statements)

References 221 publications

(257 reference statements)

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“…[36] However, the above mentioned strategy cannot be used for modeling of lipase-catalyzed reactions occurring according to a mechanism devoid of the covalent bonding of the substrate to the enzyme. This is the case in the elimination of acetic acid from 11 Ac-PGE 2 (1) catalyzed by TLL-an abnormal catalytic performance discovered by our group [1,15] -further demonstrating the intriguing promiscuity of lipases (Scheme 1). For the modeling of the reactions of this type, analysis of the docking sites and modes has to be undertaken to explain the feasibility of a certain reaction or selectivity observed.…”

Section: Introductionmentioning

confidence: 90%

“…[1] Derivatives of PGA 2 (3) have been found in high concentration in a soft coral Plexaura homomalla. [2,3] The formation of PGA 2 derivatives in corals from PGE 2 through esterase-catalyzed reactions has previously been proposed.…”

Section: Introductionmentioning

confidence: 99%

“…[1,15] The elimination mechanism has previously been expected to involve the generation and stabilization of the corresponding enolate by the lipase. [15] Modeling results on a related process catalyzed by ketosteroid isomerase [44] and also the discovery of a similar novel enzymatic acetylation-elimination process have been reported.…”

Section: Introductionmentioning

confidence: 99%

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Thermomyces lanuginosus Lipase with Closed Lid Catalyzes Elimination of Acetic Acid from 11‐Acetyl‐Prostaglandin E₂

et al. 2014

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A lipase may catalyze either one or more of the three reactions of 11‐acetyl‐prostaglandin E2 in methanol‐containing reaction medium: esterification, deacetylation, and/or elimination. The catalytic performance depends on the lipase and on the methanol content. An increase in the methanol concentration in benzene from 5 % to 95 % leads to the exclusive switch of reactions from esterification to elimination catalyzed by Thermomyces lanuginosus lipase (TLL). To explain the switch, molecular dynamics simulations of solvation of TLL in benzene and in methanol were performed. Solvation in methanol leads to the closing of the lid. The repositioning of the oxyanion hole towards the catalytic triad blocks the catalysis of ester synthesis whereas enabling TLL to act as an acetyl‐β‐ketol eliminase. In benzene the lid is open, allowing esterification to occur. Docking analysis of 11‐acetyl‐prostaglandin E2 into the active site of the solvated TLL structures suggested the occurrence of reactions in accordance with the experiment.

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Section: Introductionmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

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Thermomyces lanuginosus Lipase with Closed Lid Catalyzes Elimination of Acetic Acid from 11‐Acetyl‐Prostaglandin E₂

et al. 2014

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“…[14] Considerable effort has been devoted to their synthesis [15] and where the strategies have involved the retro-Diels-Alder step it has been accomplished by FVP [16] or the use of Lewis acids. [3,17] In addition, although Grieco et al reported use of CF 3 SO 3 H in the cycloreversion of norbornene derivatives, [17a] no further studies on the use of Brønsted acids in cycloreversions of this type of substrates have been published to date.…”

Section: Introductionmentioning

confidence: 99%

Retro‐Diels–Alder Reactions of Masked Cyclopentadienones Catalyzed by Heterogeneous Brønsted Acids

Demuynck

Levecque

Kidane³

et al. 2010

Adv Synth Catal

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Abstract:The zeolite H-Beta catalyzes the retroDiels-Alder reaction of a range of cyclopentadiene cyclo-adducts at moderate temperatures and ambient pressure, in the presence of an active dienophile. The active catalyst was identified and optimum reaction conditions established after screening a range of zeolites in the retro-Diels-Alder reaction of the cyclopentadiene adduct of cyclopentenone. Our results suggest that retro-Diels-Alder reactions of tricyclodecadienones are catalyzed by Brønsted acids and the high catalytic performance of H-Beta catalysts can be ascribed to the optimal balance between the number of acid sites and their strength as well as to the accessibility of these sites. The methodology was then applied to a series of alkyl derivatives of cyclopentadienylcyclopentenones to provide a viable alternative synthetic route to 4-alkylcyclopentenones and the versatility of the approach was demonstrated by the successful cycloreversion of N-cyclohexyl-2-azanorborn-5-ene.

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“…18 Substituted cyclopentenones are found in various naturally occurring, biologically active compounds, like pentenomycins.…”

mentioning

confidence: 99%

Ring Expansion of Cyclobutylmethylcarbenium Ions to Cyclopentane or Cyclopentene Derivatives and Metal-Promoted Analogous Rearrangements

2011

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Recent Developments in the Synthesis of Prostaglandins and Analogues

Cited by 250 publications

References 221 publications

Thermomyces lanuginosus Lipase with Closed Lid Catalyzes Elimination of Acetic Acid from 11‐Acetyl‐Prostaglandin E₂

Thermomyces lanuginosus Lipase with Closed Lid Catalyzes Elimination of Acetic Acid from 11‐Acetyl‐Prostaglandin E₂

Retro‐Diels–Alder Reactions of Masked Cyclopentadienones Catalyzed by Heterogeneous Brønsted Acids

Ring Expansion of Cyclobutylmethylcarbenium Ions to Cyclopentane or Cyclopentene Derivatives and Metal-Promoted Analogous Rearrangements

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Recent Developments in the Synthesis of Prostaglandins and Analogues

Cited by 250 publications

References 221 publications

Thermomyces lanuginosus Lipase with Closed Lid Catalyzes Elimination of Acetic Acid from 11‐Acetyl‐Prostaglandin E2

Thermomyces lanuginosus Lipase with Closed Lid Catalyzes Elimination of Acetic Acid from 11‐Acetyl‐Prostaglandin E2

Retro‐Diels–Alder Reactions of Masked Cyclopentadienones Catalyzed by Heterogeneous Brønsted Acids

Ring Expansion of Cyclobutylmethylcarbenium Ions to Cyclopentane or Cyclopentene Derivatives and Metal-Promoted Analogous Rearrangements

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Thermomyces lanuginosus Lipase with Closed Lid Catalyzes Elimination of Acetic Acid from 11‐Acetyl‐Prostaglandin E₂

Thermomyces lanuginosus Lipase with Closed Lid Catalyzes Elimination of Acetic Acid from 11‐Acetyl‐Prostaglandin E₂