2021
DOI: 10.1021/acscatal.1c03009
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Iron-Catalyzed Stereoconvergent Tertiary Alkylation of (E)- and (Z)-Mixed Internal Olefins with Functionalized Tertiary Alkyl Halides

Abstract: Herein, we report an efficient method for the stereoconvergent tertiary alkylations of (E)- and (Z)-mixed internal olefins (styrenes, enamides, and vinylic ethers) to produce trisubstituted olefins bearing a quaternary carbon center via an addition/elimination reaction in the presence of an iron catalyst. (E)- and (Z)-mixed internal olefins with various E/Z ratios reacted smoothly with α-bromocarbonyls as a tertiary alkyl source to exclusively produce (E)-trisubstituted olefins. Mechanistic studies revealed th… Show more

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Cited by 11 publications
(7 citation statements)
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“…Both isomers of the conjugated diene coordinate with the iron catalyst in a cis conformation and generate conformationally specific anti ‐π‐allyl iron intermediates via ligand‐ligand hydrogen transfer (LLHT), which ultimately determines the stereoselectivity of the reaction. The stereoconvergent mechanism disclosed in this study differs from the mechanisms of other related reactions mediated by radicals [4d] or metal‐hydride species [8] reported in other studies and can be expected to inspire the development of new stereoconvergent transformations of olefins as well as new iron‐catalyzed reactions.…”
Section: Introductionmentioning
confidence: 51%
“…Both isomers of the conjugated diene coordinate with the iron catalyst in a cis conformation and generate conformationally specific anti ‐π‐allyl iron intermediates via ligand‐ligand hydrogen transfer (LLHT), which ultimately determines the stereoselectivity of the reaction. The stereoconvergent mechanism disclosed in this study differs from the mechanisms of other related reactions mediated by radicals [4d] or metal‐hydride species [8] reported in other studies and can be expected to inspire the development of new stereoconvergent transformations of olefins as well as new iron‐catalyzed reactions.…”
Section: Introductionmentioning
confidence: 51%
“…Other notable advances in Fe-catalyzed reactions include the following publications: (1) Photoinduced iron-catalyzed ipso -nitration of aryl halides via single-electron transfer; (2) Iron-catalyzed ring-opening reactions of cyclopropanols with alkenes and TBHP: synthesis of 5-oxo peroxides; and (3) Iron-catalyzed stereoconvergent tertiary alkylation of ( E )- and ( Z ) mixed internal olefins with functionalized tertiary alkyl halides …”
Section: Recent Reports On Fe-catalyzed Reactionsmentioning
confidence: 99%
“…9 Various strategies exist for constructing alkene skeletons, and the synthesis of higher alkenes from lower ones represents a common approach to accessing complex open-chain olefins. 10 Prominent methods encompass the Heck reaction, 11 alkenyl C–H bond alkylation, 12 radical addition, 13 and electrophilic addition. 14 Transition metal catalysts, photocatalysts, radical initiators, or Lewis acid catalysts have emerged as pivotal factors in enabling these transformations.…”
Section: Introductionmentioning
confidence: 99%