First Stereoselective Total Synthesis of Isoaspinonene through a Baylis–Hillman/Olefin Cross‐Metathesis Protocol

Krishna, Palakodety Radha; Alivelu, Munagala; Rao, T. Prabhakar

doi:10.1002/ejoc.201101211

Cited by 15 publications

(3 citation statements)

References 27 publications

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“…Our preliminary studies started with radical addition reactions of selenoesters 8a and 8b with Baylis–Hillman adduct 7 . The latter was prepared in good yield with a moderate 4:1 diastereoselectivity, through the addition of acrylate ester 5 to aldehyde 6 . In contrast with earlier observations made on substrates bearing a silyl‐protected alcohol, the radical reaction carried out on free allylic alcohol 7 under the reported conditions [TTMSH, t BuON=NO t Bu (DTBHN) in benzene] led to no reaction.…”

Section: Resultsmentioning

confidence: 67%

Acyl Radical Addition to Activated Olefins: A Stereocontrolled Route to Polysubstituted Tetrahydrofurans and Lactones, and Application to the Total Synthesis of (+)‐No. 2106 A

2017

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The addition of acyl radicals to α,β‐unsaturated esters, followed by acetalization and reduction of the resulting hemiacetal was shown to provide a straightforward access to tetrahydrofurans, and fused tetrahydrofuran–lactones in good yield with high 1,3‐stereocontrol. Similar addition reactions to five‐ and six‐membered‐ring α‐methylenelactones led to trisubstituted lactones with high diastereocontrol, using (Me3Si)3SiH as hydrogen‐atom‐transfer agent. This strategy was applied to the first total synthesis of (+)‐No. 2106 A, a fused THF–lactone produced by an endophytic fungus isolated from the seeds of the mangrove Avicennia marina.

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Section: Resultsmentioning

confidence: 67%

Acyl Radical Addition to Activated Olefins: A Stereocontrolled Route to Polysubstituted Tetrahydrofurans and Lactones, and Application to the Total Synthesis of (+)‐No. 2106 A

2017

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“…Krishna and co-workers extended the application of MBH reaction for the total synthesis of isoaspinonene (235), a secondary metabolite isolated from the cultures of Aspergillus ochraceus [67]. In this case the synthesis was initiated from a chiral aldehyde 230 that could be readily generated from racemic propyleneoxide.…”

Section: Isoaspinonenementioning

confidence: 99%

Applications of Morita-Baylis-Hillman Reaction to the Synthesis of Natural Products and Drug Molecules

Bhowmik¹,

Batra

2015

COC

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The synthesis of complex natural products from simple and common intermediates has been one of the major goals in synthetic organic chemistry. Toward this objective, if such simple scaffolds are suitably decorated with diverse functional groups they present opportunities not only to synthesize the target compounds but also construct the close analogues to investigate the biological properties. The Morita-Baylis-Hillman (MBH) reaction is an organocatalyzed CC bond forming reaction that leads to multifunctional products thereby offering viable alternatives for employing them for other complexity generating reactions. This property has been extensively utilized for the synthesis of natural products of microbial, animal, terrestrial, and marine origins. Simultaneously, MBH adducts are precursors to several drug molecules or their intermediates. This comprehensive review assimilates applications of the Morita-Baylis-Hillman reaction for the synthesis of different natural products and drug molecules.

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“…The MBH derivatives have also been utilized for the total synthesis of natural products . During our previous synthetic studies based on the densely functionalized bicyclo[3.3.1]nonanes, which are a characteristic structure of the polycyclic polyprenylated acylphloroglucinols (PPAPs) family of natural product, we focused on the features of MBH derivatives, and have developed a convenient approach for the synthesis of the frameworks by conducting successive Michael reactions of cyclic β-ketoesters with MBH derivatives .…”

Section: Introductionmentioning

confidence: 99%

Enantioselective Michael Reaction of Cyclic β-Ketoesters with Morita–Baylis–Hillman Derivatives Using a Phase-Transfer Catalyst

2018

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This study aims to develop a highly enantioselective Michael reaction of cyclic β-ketoesters with Morita-Baylis-Hillman (MBH) derivatives using a phase-transfer catalyst. Cyclic β-ketoesters reacted with MBH derivatives to stereoselectively generate a quaternary carbon center in the presence of cinchona alkaloid-derived bulky ammonium catalyst, and aqueous KOH and Michael adducts bearing an acrylate moiety were obtained in good chemical yields with good enantioselectivity.

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First Stereoselective Total Synthesis of Isoaspinonene through a Baylis–Hillman/Olefin Cross‐Metathesis Protocol

Abstract: The first stereoselective and efficient total synthesis of isoaspinonene by using Baylis–Hillman reaction, chelation‐controlled vinyl Grignard reaction, Wittig olefination, and olefin cross‐metathesis reaction of a hitherto unreported substrate as the key steps is described.

Cited by 15 publications

References 27 publications

Acyl Radical Addition to Activated Olefins: A Stereocontrolled Route to Polysubstituted Tetrahydrofurans and Lactones, and Application to the Total Synthesis of (+)‐No. 2106 A

Acyl Radical Addition to Activated Olefins: A Stereocontrolled Route to Polysubstituted Tetrahydrofurans and Lactones, and Application to the Total Synthesis of (+)‐No. 2106 A

Applications of Morita-Baylis-Hillman Reaction to the Synthesis of Natural Products and Drug Molecules

Enantioselective Michael Reaction of Cyclic β-Ketoesters with Morita–Baylis–Hillman Derivatives Using a Phase-Transfer Catalyst

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