Base-Catalyzed Diels−Alder Reactions of 2<i>H</i>-Pyran-2,5-diones: A Mild Approach to Basiliolide B

Zhou, Xiongfei; Wu, Wanqing; Liu, Xiaozu; Lee, Chi‐Sing

doi:10.1021/ol8022787

Cited by 52 publications

(15 citation statements)

References 39 publications

(15 reference statements)

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“…More interestingly, the basiliolides and transtaganolides contain an unprecedented 7‐methoxy‐4,5‐dihydro‐3 H ‐oxepin‐2‐one (C ring). Due to the unique structural features and the interesting biological activities, a considerable amount of efforts toward the biosynthesis and biomimetic synthesis of the basiliolide/transtaganolide family have been reported 4–8. As shown in Figure 1, an Ireland–Claisen rearrangement of prenyl 2‐pyrone 2 (isolated along with the transtaganolides by Massanet’s group) followed by an intramolecular 2‐pyrone Diels–Alder (DA) cycloaddition sequence has been proposed for the biosynthesis of the tricyclic core structure of transtaganolide E and F, which are the seco acid derivatives of transtaganolide D and C (basiliolide A1 and A2) 4.…”

Section: Methodsmentioning

confidence: 99%

A Biomimetic Synthesis of (±)‐Basiliolide B

et al. 2014

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A highly diastereoselective and practical biomimetic total synthesis of (±)-basiliolide B has been achieved through the study of the two proposed biosynthetic pathways (O-methylation and O-acylation) for the unprecedented 7-methoxy-4,5-dihydro-3H-oxepin-2-one (C ring). The synthesis featured a cyclopropanation/ring opening strategy for establishing the stereogenic centers at C8 and C9, a biomimetic 2-pyrone Diels-Alder cycloaddition for the synthesis of the ABD ring system, and finally a highly efficient biomimetic intramolecular O-acylation for the C ring formation. This result provides an important perspective on the biosynthetic origin of the unprecedented 7-membered acyl ketene acetal moiety of the C ring.

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Section: Methodsmentioning

confidence: 99%

A Biomimetic Synthesis of (±)‐Basiliolide B

et al. 2014

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“…[4a] This reaction was first reported by Nakatanis group using a Brønsted base as the catalyst in 1995. [6] In the course of developing new methods for construction of the tricyclic core of basiliolide B, [7] we have found that 2H-pyran-2,5-diones can be used as a synthon of 5-hydroxy-2-pyrones for DA cycloadditions. [6] In the course of developing new methods for construction of the tricyclic core of basiliolide B, [7] we have found that 2H-pyran-2,5-diones can be used as a synthon of 5-hydroxy-2-pyrones for DA cycloadditions.…”

Section: Introductionmentioning

confidence: 99%

A New Class of Enantioselective Catalytic 2‐Pyrone Diels–Alder Cycloadditions

Min

Zhu

et al. 2011

Adv Synth Catal

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A highly enantioselective catalytic DielsAlder (DA) cycloaddition of 2H-pyran-2,5-diones (synthon of 5-hydroxy-2-pyrones) has been developed with a Cinchona-derived thiourea as the catalyst. The conditions were optimized by using 0.2 equiv. of the catalyst and 0.1 equiv. of formic acid in 2-propanol at room temperature, which afforded the DA products in yields of up to 90% (exo/endo = 5.5:1, 98% ee) with trans-b-nitrostyrene derivatives as the dienophiles. The structure/activity relationships of the bifunctional catalyst and the effects of the steric, electronic and hydrogen-bonding properties of the dienophiles have been studied.

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“…In the course of this study, we have found that 2H-pyran-2,5-diones can be converted into 5-hydroxy-2-pyrones by treatment with catalytic amounts of base and undergo DA cycloaddition with acrylates at room temperature in a one-pot manner. [12] Here we disclose our full study of this new class of 2-pyrone DA cycloadditions, in which both the 2H-pyran-2,5-dione 1 and the 5-(tert-butyldimethylsilyloxy)-2-pyrone 2 can be utilized as synthons for 5-hydroxy-2-pyrones for DA cycloaddition (Scheme 2). …”

Section: Introductionmentioning

confidence: 99%

Diels–Alder Cycloadditions of 5‐Hydroxy‐2‐pyrones: 2H‐Pyran‐2,5‐diones and 5‐(tert‐Butyldimethylsilyloxy)‐2‐pyrones as Synthons

Zhou

et al. 2010

Eur J Org Chem

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Diels–Alder (DA) cycloadditions of 5‐hydroxy‐2‐pyrones based on the use of 2H‐pyran‐2,5‐diones and 5‐(tert‐butyldimethylsilyloxy)‐2‐pyrones as synthons have been developed. Upon treatment either with a base or with a Lewis acid, 2H‐pyran‐2,5‐diones equilibrated to 5‐hydroxy‐2‐pyrones and underwent DA cycloaddition. The base‐catalyzed protocol was optimized with cHex2NMe (0.1 equiv.) in tBuOH at room temperature, which gave the bicyclic cycloadducts in yields of up to 81 % (endo/exo = 6.2:1). The Lewis‐acid‐promoted protocol was optimized by conversion of 2H‐pyran‐2,5‐diones into 5‐(tert‐butyldimethylsilyloxy)‐2‐pyrones and use of BF3·OEt2, which afforded the same DA products in yields of up to 90 % (endo/exo = 12:1).

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Base-Catalyzed Diels−Alder Reactions of 2H-Pyran-2,5-diones: A Mild Approach to Basiliolide B

Cited by 52 publications

References 39 publications

A Biomimetic Synthesis of (±)‐Basiliolide B

A Biomimetic Synthesis of (±)‐Basiliolide B

A New Class of Enantioselective Catalytic 2‐Pyrone Diels–Alder Cycloadditions

Diels–Alder Cycloadditions of 5‐Hydroxy‐2‐pyrones: 2H‐Pyran‐2,5‐diones and 5‐(tert‐Butyldimethylsilyloxy)‐2‐pyrones as Synthons

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