Synthesis of Chiral 2,3-Dihydrofurans via One-Pot Pd-Catalyzed Asymmetric Allylic Cycloaddition and a Retro-Dieckmann Fragmentation Cascade

Shah, Babar Hussain; Khan, Sardaraz; Zhao, Can; Zhang, Yong Jian

doi:10.1021/acs.joc.3c00976

Cited by 5 publications

(2 citation statements)

References 47 publications

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“…Khan reported an efficient method for construction of furanobenzodihydropyran through Pd-catalyzed asymmetric decarboxylative cycloaddition of vinylethylene carbonates with 3-cyanochromones [12]. Shah enabled enantioselective synthesis of 2,3-dihydrofurans bearing quaternary stereocenter via Pd-catalyzed asymmetric cascade allylic cycloaddition and retro-Dieckmann Fragmentation [13]. Then numerous electrophiles appeared such as iso(thio)-cyanate in formal [3+2] cycloaddition for synthesis of 1,3-oxazolidine-2-thione [14], 2-arylidene-1,3-indandione in asymmetric [3+2] cycloaddition to form tetrahydrofuran-fused spirocyclic 1,3-indandione [15], isatin in decarboxylative [3+2] cycloaddition to generate functionalized spirooxindole [16], and methyleneindolinone in assembly of structurally diverse 3,3′-tetrahydrofuryl spirooxindole [17].…”

Section: Introductionmentioning

confidence: 99%

Theoretical investigation on diastereoselective [2+2] cycloaddition and Pd-catalyzed enantioselective [3+2] cycloaddition for synthesis of cis-β-lactam and exo-furobenzopyranone

Lu,

Miao,

Lan

2024

Therm. Sci. Eng.

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The mechanism is investigated for Wolff rearrangement/Staudinger [2+2] cycloaddition cascade and Pd-catalyzed, decarboxylative, formal [3+2] cycloaddition. Wolff rearrangement of 3-diazotetramic acid is determined to be rate-limiting step generates cyclic acyl ketene. The interaction of ketene with imine firstly results in zwitterion followed by conrotatory cyclization giving major cis-β-lactam. For synthesis of s-VECs, the epoxidation−cyclization cascade and hydrolysis give precursor of better performing exocyclic derivative. The reaction with 3-cyanochromone includes decarboxylation, nucleophilic attack and subsequent ring closure yielding 5-exo-trig furobenzopyranone. Based on the comparison between possible paths, the diastereoselectivity of cis over trans and regio-divergence of 5-exo-trig over 7-endo-trig are both kinetically controlled for [2+2] and [3+2] cycloaddition in common. The positive solvation effect is suggested by decreased absolute and activation energies in chlorobenzene and chloroform solution compared with in gas. These results are supported by Multiwfn analysis on FMO composition of specific TSs, and MBO value of vital bonding, breaking.

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Section: Introductionmentioning

confidence: 99%

Theoretical investigation on diastereoselective [2+2] cycloaddition and Pd-catalyzed enantioselective [3+2] cycloaddition for synthesis of cis-β-lactam and exo-furobenzopyranone

Lu,

Miao,

Lan

2024

Therm. Sci. Eng.

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“…Especially the pioneering works of Tamaru et al . and the recent results published by Khan et al enabled the addition of numerous electrophiles, e.g., chromones, , iso(thio)cyanates, , (cyclic) imines, , barbiturate-derived alkenes, ketenes, amine-substituted enones, indandiones, isatins, methyleneindolinones, and more . However, structural variations on the nucleophilic oxa-Pd–allyl complex are scarce as a result of the challenging derivatization of VECs (Scheme A).…”

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confidence: 99%

Preparation of Spirocyclic Vinylic Carbonates from Allylic Alcohols

Topp,

Metzler,

Dressler

et al. 2024

Org. Lett.

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We present the synthesis of exo- and endo-spirovinylethylene carbonates, starting from various cyclic allylic alcohols. This one-pot cascade reaction to the spirocyclic scaffold was optimized using a design of experiments approach. The introduction of spirovinylethylene carbonates broadens the scope of using these in catalytic applications and provides an easy synthetic entry into spirocyclic scaffolds of various ring sizes.

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Chemo‐, Regio‐ and Stereoselective Preparation of (Z)‐2‐Butene‐1,4‐Diol Monoesters via Pd‐Catalyzed Decarboxylative Acyloxylation

Cheng,

Zhao,

Zhang

et al. 2024

Chemistry A European J

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(Z)‐alkenes are useful synthons but thermodynamically less stable than their (E)‐isomers and typically more difficult to prepare. The synthesis of 1,4‐hetero‐bifunctionalized (Z)‐alkenes is particularly challenging due to the inherent regio‐ and stereoselectivity issues. Herein we demonstrate a general, chemoselective and direct synthesis of (Z)‐2‐butene‐1,4‐diol monoesters. The protocol operates within a Pd‐catalyzed decarboxylative acyloxylation regime involving vinyl ethylene carbonates (VECs) and various carboxylic acids as the reaction partners under mild and operationally attractive conditions. The newly developed process allows access to a structurally diverse pool of (Z)‐2‐butene‐1,4‐diol monoesters in good yields and with excellent regio‐ and stereoselectivity. Various synthetic transformations of the obtained (Z)‐2‐butene‐1,4‐diol monoesters demonstrate how these synthons are of great use to rapidly diversify the portfolio of these formal desymmetrized (Z)‐alkenes.

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Synthesis of Chiral 2,3-Dihydrofurans via One-Pot Pd-Catalyzed Asymmetric Allylic Cycloaddition and a Retro-Dieckmann Fragmentation Cascade

Cited by 5 publications

References 47 publications

Theoretical investigation on diastereoselective [2+2] cycloaddition and Pd-catalyzed enantioselective [3+2] cycloaddition for synthesis of cis-β-lactam and exo-furobenzopyranone

Theoretical investigation on diastereoselective [2+2] cycloaddition and Pd-catalyzed enantioselective [3+2] cycloaddition for synthesis of cis-β-lactam and exo-furobenzopyranone

Preparation of Spirocyclic Vinylic Carbonates from Allylic Alcohols

Chemo‐, Regio‐ and Stereoselective Preparation of (Z)‐2‐Butene‐1,4‐Diol Monoesters via Pd‐Catalyzed Decarboxylative Acyloxylation

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