Synthesis of <i>gem‐</i>Difluorinated Cyclopropanes and Cyclopropenes: Trifluoromethyltrimethylsilane as a Difluorocarbene Source

Wang, Fei; Luo, Tao; Hu, Jinbo; Wang, Ying; Krishnan, Hema S.; Jog, Parag V.; Ganesh, Sivagini; Prakash, G. K. Surya; Oláh, George A.

doi:10.1002/ange.201101691

Cited by 87 publications

(56 citation statements)

References 45 publications

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“…Our research group recently demonstrated that singlet CF 2 carbene can be generated from TMSCF 3 in the presence of tetra‐ n ‐butylammonium difluorotriphenylsilicate (TBAT) and NaI 14. This carbene adds readily across an alkene or alkyne by a [2+1] cycloaddition reaction.…”

Section: Methodsmentioning

confidence: 99%

Copper‐Mediated Difluoromethylation of (Hetero)aryl Iodides and β‐Styryl Halides with Tributyl(difluoromethyl)stannane

et al. 2012

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Section: Methodsmentioning

confidence: 99%

Copper‐Mediated Difluoromethylation of (Hetero)aryl Iodides and β‐Styryl Halides with Tributyl(difluoromethyl)stannane

et al. 2012

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“…Since cyclopropanes [33] and fluorine [34] are of high interest in medicinal chemistry,w ew anted to see if our new compound class could be subjected to the convenient difluorocyclopropanation established by Prakashe tal. [35] To our delight we found that 3m cleanly converts to the desired geminal difluorocyclopropane 7m in good yield. For 3c,o nt he other hand, the more complex product 7c was isolated in good yield (Scheme7).…”

Section: Resultsmentioning

confidence: 88%

Synthesis of Fulvene Vinyl Ethers by Gold Catalysis

Ahrens

Schwarz

Lustosa

et al. 2020

Chemistry A European J

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Gold-catalyzed cyclization of 1,5-diynesw ith ketones as reagents and solvent provides diversely substituted vinyl ethers under mild conditions. The regioselectivity of such gold-catalyzed cyclizations is usually controlled by the scaffold of the diyne. Herein, we report the first solvent-controlled switchingo fr egioselectivity from a6 -endo-dig-to 5endo-dig-cyclization in these transformations,p roviding fulvene derivatives. With respectt ot he functional-group toler-ance, aryl fluorides, chlorides, bromides,and ethers are tolerated. Furthermore, the mechanism and selectivity are put to scrutinyb ye xperimental studies and at hermodynamic analysis of the product. Additionally,6 -(vinyloxy)fulvenesa re a hitherto unknown class of compounds. Theirr eactivity is briefly evaluated, to give insights into their potential applications.[ + + ] Crystallographic investigation;T heoreticali nvestigation Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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“…Most importantly, it is not limited to free carbenes; metallocarbenoids also readily undergo reaction with alkynes, with dirhodium(II) catalyst being the most efficient for cyclopropenation of terminal alkynes using the corresponding diazo compounds 14 to form the cyclopropene with the desired C3-substitution pattern. This method, however, does not work well for halocarbenes, as their metallocarbenoids react differently with terminal alkynes, 15 so 3,3-difluorocyclopropenes were synthesized by addition of the difluorocarbene, generated in situ, 16 to the alkynes (Scheme 1). Furthermore, 1-(trimethylsilyl)cyclopropene 17 can be easily converted into 1,2-non-substituted cyclopropenes by hydrolysis in mild basic conditions.…”

Section: Resultsmentioning

confidence: 99%

“…22 General procedure for difluorocarbene addition to a carbon-carbon triple bond. 16 Appropriate alkyne (1 eq), anhydrous NaI (2.2 eq), TMSCF 3 (2 eq) were dissolved in anhydrous THF.…”

Section: H Nmr (Cdcl 3 400 Mhz): δ 384 (S 6 H)mentioning

confidence: 99%

Cyclopropenes as Potential Warheads for Inhibitors of Cysteine Proteases

Gurjar¹,

Bercz²,

Nguyen³

et al. 2015

ujc

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Over expression of cysteine proteases in human body causes neurodegenerative diseases, destruction of cartilage tissue, and bone atrophy, and some of them are implicated in destructive role of malignant tumors and cancer metastasis. Several non-human cysteine proteases play a key role in life cycles of certain foreign invasive organisms. Therefore, inhibition of cysteine proteases represents an important venue for finding potential therapeutic agents against Alzheimer's disease, multiple sclerosis, ischemic stroke, myocardial infarcts, carcinoma progression, as well as some parasital and viral infections. Affinity labeling agents used as inhibitors of cysteine proteases normally bear an electrophilic "warhead", a reactive group that covalently binds the active site cysteine residue thereby inactivating the enzyme, but achieving both high activity and selectivity remains challenging. We are developing cyclopropene derivatives that show selective binding of thiol residues of cysteine. Several derivatives of cyclopropenes have been synthesized and evaluated as potential cysteine-binding "warheads". Their stability in aqueous media and reactivity toward cysteine and other amino acid chemical probes was examined. We have found that 1,2-cyclopropene moiety irreversibly binds the thiol group of cysteine, leaving other amino acid residues unaffected, which has the advantage for targeting enzymes expressed in foreign organisms or promoting carcinoma progression.

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Synthesis of gem‐Difluorinated Cyclopropanes and Cyclopropenes: Trifluoromethyltrimethylsilane as a Difluorocarbene Source

Cited by 87 publications

References 45 publications

Copper‐Mediated Difluoromethylation of (Hetero)aryl Iodides and β‐Styryl Halides with Tributyl(difluoromethyl)stannane

Copper‐Mediated Difluoromethylation of (Hetero)aryl Iodides and β‐Styryl Halides with Tributyl(difluoromethyl)stannane

Synthesis of Fulvene Vinyl Ethers by Gold Catalysis

Cyclopropenes as Potential Warheads for Inhibitors of Cysteine Proteases

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