2022
DOI: 10.1021/acs.orglett.2c02362
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Zinc-Mediated Transformation of 1,3-Diols to Cyclopropanes for Late-Stage Modification of Natural Products and Medicinal Agents

Abstract: A method for incorporating cyclopropane motifs into complex molecules has been developed. Herein we report a zinc dust-mediated cross-electrophile coupling reaction of 1,3-dimesylates to synthesize cyclopropanes. 1,3-Dimesylates can be readily accessed from 1,3-diols, a functionality prevalent in many natural products and medicinal agents. The reaction conditions are mild, such that functional groups, including amides, esters, heterocycles, and alkenes, are tolerated. Notably, we have demonstrated late-stage c… Show more

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Cited by 7 publications
(6 citation statements)
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References 56 publications
(34 reference statements)
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“…The catalytic cycle can be divided into two parts: (1) formation of the 1,3-diiodide intermediate and (2) Ni-catalyzed XEC reaction. Our previous study provided evidence that 1,3-diiodides are formed in situ from 1,3-dimesylates before entering the nickel catalytic cycle. , Therefore, the Ni-catalyzed XEC reaction begins with the active catalyst Ni 0 L n , A , and 1,3-diiodide. Halogen atom transfer (XAT) occurs to generate Ni­(I) species B and secondary alkyl radical C .…”
Section: Resultsmentioning
confidence: 99%
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“…The catalytic cycle can be divided into two parts: (1) formation of the 1,3-diiodide intermediate and (2) Ni-catalyzed XEC reaction. Our previous study provided evidence that 1,3-diiodides are formed in situ from 1,3-dimesylates before entering the nickel catalytic cycle. , Therefore, the Ni-catalyzed XEC reaction begins with the active catalyst Ni 0 L n , A , and 1,3-diiodide. Halogen atom transfer (XAT) occurs to generate Ni­(I) species B and secondary alkyl radical C .…”
Section: Resultsmentioning
confidence: 99%
“…The reaction with 1,3-dimesylate 1 was chosen as our computational model (eq ). Key questions included the identity of the nucleophilic iodide source and stereochemical outcome of iodide formation. …”
Section: Resultsmentioning
confidence: 99%
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“…24 After evaluation of a series of reaction conditions, we determined that zinc powder, in the absence of a nickel catalyst, was capable of transforming dimesylates to cyclopropanes (Scheme 14). 34 Critical to the reaction was addition of stoichiometric quantities of an iodide salt, NaI, consistent with formation of alkyl iodides in situ as key intermediates. With these reaction conditions, we can engage a range of substrates bearing sensitive functional groups including a series derived from statins.…”
Section: Part Ii: Stereoablative Reactions Of Alcohol Derivativesmentioning
confidence: 99%