Synthesis and properties of trans 1-aryl-2-benzoylcyclopropanes and their vinyloges

Yanovskaya, L. A.; Dombrovsky, V.A.; Chizhov, O. S.; Zolotarev, B. M.; Subbotin, O. A.; Kucherov, V. F.

doi:10.1016/0040-4020(72)88038-4

Cited by 17 publications

(5 citation statements)

References 12 publications

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“…Due to this, epoxidation is preferred over the cyclopropanation. This is consistent with the experimental observations …”

Section: Resultssupporting

confidence: 94%

“…Consequently, the rate‐determining transition state TS4 in epoxidation pathway is higher than TS1 of the irreversible 1,4‐addition transition state in cyclopropanation pathway by 5.5 kcal/mol, and cyclopropanation is preferred over the epoxidation. This is consistent with the experimental observations …”

Section: Resultssupporting

confidence: 94%

“…Under standard reaction conditions, the reactions of both DMSM and DMSOM in DMSO solution toward ordinary aldehydes and ketones gave only epoxidation products. However, when these two ylides reacted with α,β‐unsaturated carbonyl compounds such as chalcone, different products were generated (Scheme ) , . Reactions of DMSOM with enones gave cyclopropanation products, while the reactions of DMSM with enones still produced epoxidation products (similar to their reactions with aldehydes and ketones).…”

Section: Introductionmentioning

confidence: 99%

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Understanding Regioselectivities of Corey–Chaykovsky Reactions of Dimethylsulfoxonium Methylide (DMSOM) and Dimethylsulfonium Methylide (DMSM) toward Enones: A DFT Study

et al. 2018

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The Corey–Chaykovsky reaction, using either in situ generated dimethylsulfoxonium methylide (DMSOM) or dimethylsulfonium methylide (DMSM) to react with ketones or aldehydes, is widely used in the synthesis of epoxides. However, when DMSOM and DMSM react with enones (such as chalcone), the former reactions give cyclopropanation products whereas the latter reactions still generate epoxides. DFT calculations have been carried out to understand these different regioselectivities. We found that the cyclopropanation pathways for both DMSOM and DMSM toward chalcone (a model for enones) start with rate‐determining and irreversible 1,4‐addition reactions, followed by easier intramolecular substitution reactions to give cyclopropanes. The overall activation free energies for cyclopropanation are 17.5 and 15.5 kcal/mol for DMSOM and DMSM, respectively. The epoxidation pathways for both DMSOM and DMSM have reversible 1,2‐addition reactions, followed by rate‐determining intramolecular substitution reactions to give epoxides. The computed barriers for the epoxidation are 23.0 and 13.3 kcal/mol for DMSOM and DMSM, respectively. Therefore, the cyclopropanation pathway is favored for DMSOM while epoxidation is preferred for DMSM. We attribute these different reaction scenarios to thermodynamic reasons that DMSOM is more stable than DMSM. The reaction pathways for reactions of other derivatives of DMSM toward enones have also been discussed.

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“…Due to this, epoxidation is preferred over the cyclopropanation. This is consistent with the experimental observations …”

Section: Resultssupporting

confidence: 94%

Section: Resultssupporting

confidence: 94%

Section: Introductionmentioning

confidence: 99%

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Understanding Regioselectivities of Corey–Chaykovsky Reactions of Dimethylsulfoxonium Methylide (DMSOM) and Dimethylsulfonium Methylide (DMSM) toward Enones: A DFT Study

et al. 2018

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“…Next, we examined the [3 + 2] cycloaddition of silyl enol ethers 1 with trans-2-(p-methoxyphenyl)cyclopropyl phenyl ketone (trans-5) [15] as D-A cyclopropane. The p-methoxyphenyl group corresponds to a weaker electron-donating group, as opposed to the alkoxyl and alkylthio groups.…”

mentioning

confidence: 99%

Construction of Highly‐Functionalized Cyclopentanes from Silyl Enol Ethers and Activated Cyclopropanes by [3+2] Cycloaddition Catalyzed by Triflic Imide

2006

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[1] Donor-acceptor (D-A) substituted cyclopropanes [2,3] are utilized as equivalents of three carbon 1,3-dipole unit for the formation of 5-membered carbocyles. Kuwajima and his co-workers reported that [3 + 2] cycloadditions of D-A cyclopropanes, such as 2-alkoxy-and 2-phenylthiocyclopropyl carbonyl compounds, with silyl enol ethers were promoted by SnCl 4 [4] and Me 2 AlCl, [5] respectively, to furnish multi-functionalized cyclopentanes. Although several such [3 + 2] cycloadditions have been documented using various substances after their findings, [2,6,7] most of them require a stoichiometric amount of Lewis acid, except for a few exceptions. [4,8] As a part of our ongoing research program on catalytic [2 + 2] cycloaddition of silyl enol ethers to construct highly-substituted cyclobutanes, [9] we recently found that triflic imide (Tf 2 NH) [10] efficiently catalyzes the [2 + 2] cycloaddition.[11] We have demonstrated that silyl triflic imide (R 3 SiNTf 2 ), [12] which is generated in situ from Tf 2 NH with silyl enol ethers, acts as the actual catalyst. We expected that Tf 2 NH would be a new possibility for good catalysis of At the outset of this study, the [3 + 2] cycloaddition of TBS enol ether (1a) with trans-ethyl 2-butoxycyclopropanecarboxylate (trans-2a) [4] as D-A cyclopropane was examined using several fluorinated Brønsted acid catalysts (Table 1, entries 1-4). Treatment of trans-2a with TBS enol ether 1a in the presence of Tf 2 NH (1 mol %) in CH 2 Cl 2 at À78 8C for 2 h afforded the highly-substituted cyclopentane product 3a in 69 % yield as a mixture of four diastereomers (entry 1). [13] In contrast, the reaction using a stoichiometric amount of Tf 2 NH resulted in only a trace yield of 3a and decomposition of 1a (entry 2). Imide 4, [14] which is the cyclic analogue of Tf 2 NH, also acts as a good catalyst (entry 4), whereas triflic acid (TfOH) does not promote the cycloaddition (entry 3).As shown in Table 1 (entries 5-9), [3 + 2] cycloaddition of 1 with trans-2a proceeded smoothly by addition of a catalytic amount (1 mol %) of Tf 2 NH to afford highly-functionalized cyclopentanes 3 in good yield. In contrast, the reaction of TMS enol ether 1b afforded 3b in 9 % yield, along with desilylated product in 60 % yield (entry 5). We have examined the 2376

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“…The effect of cis-trans geometry was noted in a dc and cv study of dibenzoyl-styrene, -ethylene, -stilbene, -cyclopropane, -phenylcyclopropane, and -diphenylcyclopropane (1188). Polarographic data were reported for transl-aryl-2-benzoyl cyclopropane and substituted derivatives (1193) and fori, 0 where Z = -CH2S-, -OCH2-, -CH2- (446). Oxidation data for dimercaptothiopyrone derivatives, II, were studied at a graphite electrode (35).…”

Section: Ketonesmentioning

confidence: 99%

Organic polarography

Pietrzyk¹

1974

Anal. Chem.

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Chemical Titles, and readily available journals ending November 30, 1973. This period has seen a continued growth in the use of polarography and related electrochemical techniques to follow chemical reactions and to supplement other physical and spectral measurements for purposes of characterization. Interest in applications toward biochemical and pharmaceutical problems has also increased. There also appears to be renewed interest in utilizing polarographic and related electrochemical data to predict and follow organoelectrochemical synthesis.In this review the symbols cv, dc, ac, and op are used to identify cyclic voltammetry, direct current polarography, alternating current polarography, and oscillographic polarography, respectively. Also, no attempt was made to list all organic polarographic references.

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Synthesis and properties of trans 1-aryl-2-benzoylcyclopropanes and their vinyloges

Cited by 17 publications

References 12 publications

Understanding Regioselectivities of Corey–Chaykovsky Reactions of Dimethylsulfoxonium Methylide (DMSOM) and Dimethylsulfonium Methylide (DMSM) toward Enones: A DFT Study

Understanding Regioselectivities of Corey–Chaykovsky Reactions of Dimethylsulfoxonium Methylide (DMSOM) and Dimethylsulfonium Methylide (DMSM) toward Enones: A DFT Study

Construction of Highly‐Functionalized Cyclopentanes from Silyl Enol Ethers and Activated Cyclopropanes by [3+2] Cycloaddition Catalyzed by Triflic Imide

Organic polarography

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