Lewis Acid-Mediated Ring-Opening Reactions of trans-2-Aroyl-3-styrylcyclopropane-1,1-dicarboxylates: Access to Cyclopentenes and E,E-1,3-Dienes

Thangamani, Murugesan; Srinivasan, Kannupal

doi:10.1021/acs.joc.7b02335

Cited by 26 publications

(5 citation statements)

References 43 publications

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“…When the solvent was switched to 1,2-DCE, the reaction took place, but the expected product 5a was obtained only in 12% yield (entry 2). When the reaction was carried out using 1 equiv of SnCl 4 in 1,2-DCE at room temperature, instead of forming product 5a , DAC 3a underwent fragmentation (with the assistance of moisture) to yield indanedionyl malonate 9 and benzaldehyde (entry 3). ,, This type of fragmentation was also observed when BF 3 ·OEt 2 or GaCl 3 was used as the Lewis acid (entries 4 and 5). When FeCl 3 was used as the Lewis acid in the reaction, the expected product 5a was obtained in 35% yield (entry 6).…”

Section: Resultsmentioning

confidence: 90%

Intramolecular 1,2-Aroyl Migration in Spiro Donor–Acceptor Cyclopropanes: Formation of 1,4-Naphthoquinones and 1-Naphthols as Ring-Expansion Products

Daniel,

Srinivasan

2024

J. Org. Chem.

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Most of the known rearrangement reactions of donor−acceptor cyclopropanes (DACs) involve the migration of cationic carbon atom to anionic carbon or heteroatoms in 1,3-or 1,4-positions. In the present work, we observed that spiro DACs based on 1,3-indanedione or 1-indanone moiety undergo intramolecular 1,2-aroyl migration when treated with titanium(IV) chloride to afford 1,4-naphthoquinones and α-naphthols readily. The reactions take place through the formation of putative 1,3-dipolar intermediates, followed by cleavage and migration of the aroyl group to the adjacent carbon to afford the ring-expansion products.

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Section: Resultsmentioning

confidence: 90%

Intramolecular 1,2-Aroyl Migration in Spiro Donor–Acceptor Cyclopropanes: Formation of 1,4-Naphthoquinones and 1-Naphthols as Ring-Expansion Products

Daniel,

Srinivasan

2024

J. Org. Chem.

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“…The allylic transposition of alkyl groups is a highly desirable synthetic transformation that enables the rearrangement of C–C bonds in intricate compounds. While thermal [1s,3s] alkyl shifts are not feasible because of orbital symmetry restrictions, several alkyl 1,3-transpositions have been observed through sequential pathways involving the cleavage and reformation of C–C bonds. − Through consecutive carbon–carbon bond cleavage and recombination steps, the Knowles group developed a proton-coupled electron transfer (PCET)-based, light-driven strategy for the 1,3-transposition of acyclic allylic alcohols. Here, the substrate is oxidized by the excited iridium photocatalyst to produce a radical cation intermediate A .…”

Section: Cleavage Of Carbon–carbon Single Bondmentioning

confidence: 99%

Carbon–Carbon Bond Cleavage for Late-Stage Functionalization

Liang,

Bilal,

Tang

et al. 2023

Chem. Rev.

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Late-stage functionalization (LSF) introduces functional group or structural modification at the final stage of the synthesis of natural products, drugs, and complex compounds. It is anticipated that late-stage functionalization would improve drug discovery’s effectiveness and efficiency and hasten the creation of various chemical libraries. Consequently, late-stage functionalization of natural products is a productive technique to produce natural product derivatives, which significantly impacts chemical biology and drug development. Carbon–carbon bonds make up the fundamental framework of organic molecules. Compared with the carbon–carbon bond construction, the carbon–carbon bond activation can directly enable molecular editing (deletion, insertion, or modification of atoms or groups of atoms) and provide a more efficient and accurate synthetic strategy. However, the efficient and selective activation of unstrained carbon–carbon bonds is still one of the most challenging projects in organic synthesis. This review encompasses the strategies employed in recent years for carbon–carbon bond cleavage by explicitly focusing on their applicability in late-stage functionalization. This review expands the current discourse on carbon–carbon bond cleavage in late-stage functionalization reactions by providing a comprehensive overview of the selective cleavage of various types of carbon–carbon bonds. This includes C–C(sp), C–C(sp2), and C–C(sp3) single bonds; carbon–carbon double bonds; and carbon–carbon triple bonds, with a focus on catalysis by transition metals or organocatalysts. Additionally, specific topics, such as ring-opening processes involving carbon–carbon bond cleavage in three-, four-, five-, and six-membered rings, are discussed, and exemplar applications of these techniques are showcased in the context of complex bioactive molecules or drug discovery. This review aims to shed light on recent advancements in the field and propose potential avenues for future research in the realm of late-stage carbon–carbon bond functionalization.

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“…王忠文等 [44] 开发了 Sc(OTf [45] 又开发了路易斯酸催化的环丙烷-1,1-二酯与丙二烯的分子内[3＋2]扩环反应(Scheme 11). 与上一个反应 [44] 2018 年, Thangamani 等 [46] 也报道了环丙烷- 与反式(E)-醛亚胺的动态动力学不对称环化, 并制备得到了 2,5-顺式-二取代吡咯烷(Eq. 9).…”

Section: Arunclassified

Recent Progress on[3+2] Ring-Expansion Reaction of Cyclopropane with Unsaturated Compounds

Liu¹,

Dou²,

Mu³

2020

Chin. J. Org. Chem.

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Due to its high ring strain, cyclopropanes can react with a variety of unsaturated compounds to construct fivemembered carbo-and hetero-cycles through [3＋2] ring-expansion reaction. These five-membered compounds are key skeletons of many drugs, natural products and bioactive molecules, and are also an important class of organic intermediates which have wide applications in medicine, agriculture, chemical engineering, organic synthesis and other related areas. Recently, more and more chemists have constructed a lot of complex five-membered carbo-and hetero-cycles by using cyclopropane as a three-carbon synthon, which has promoted the rapid development of focus area. This review summarizes the most recent [3＋2] ring-expansion reaction of cyclopropanes with compounds containing unsaturated bonds such as olefins, aldehydes, ketones and nitriles in the past decade. Moreover, the prospects of future development are also discussed. Keywords cyclopropane; unsaturated bond; [3＋2] ring-expansion reaction; five-membered ring 环丙烷是结构最简单的环烷烃, 由于其环 C-C 的键角远远小于正常 C(sp 3 )-C(sp 3 )的键角, 导致其键角的弯曲程度增大, 因此具有很强的环张力 [1～3] (应变能为 121.4 kJ•mol -1 [3] ). 环丙烷可被具有不同电子特性的基团取代, 并生成一系列环丙烷衍生物. 经实验测定和理论计算 [2][3][4]

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Lewis Acid-Mediated Ring-Opening Reactions of trans-2-Aroyl-3-styrylcyclopropane-1,1-dicarboxylates: Access to Cyclopentenes and E,E-1,3-Dienes

Cited by 26 publications

References 43 publications

Intramolecular 1,2-Aroyl Migration in Spiro Donor–Acceptor Cyclopropanes: Formation of 1,4-Naphthoquinones and 1-Naphthols as Ring-Expansion Products

Intramolecular 1,2-Aroyl Migration in Spiro Donor–Acceptor Cyclopropanes: Formation of 1,4-Naphthoquinones and 1-Naphthols as Ring-Expansion Products

Carbon–Carbon Bond Cleavage for Late-Stage Functionalization

Recent Progress on[3+2] Ring-Expansion Reaction of Cyclopropane with Unsaturated Compounds

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