Metal‐Free Enantioselective Oxidative Arylation of Alkenes: Hypervalent‐Iodine‐Promoted Oxidative C−C Bond Formation

Shimogaki, Mio; Fujita, Morifumi; Sügimura, Takashi

doi:10.1002/ange.201609110

Cited by 10 publications

(9 citation statements)

References 71 publications

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“…3a,3b,34 More recently, Fujita and co-workers also reported that such a I(III) + ⋯O interaction exists even in acetonitrile. 6b The formation of the strong I(III) + ⋯O interaction in 1a+ induces a conformational change of the benzylic group, resulting in disruption of halogen-π interactions and exposure of the highly electrophilic cationic I(III) center for subsequent substrate binding and activation.…”

Section: Resultsmentioning

confidence: 99%

“…The discovery of enantioselective molecular catalysts based on iodine (I/III) redox chemistry has added a new dimension to hypervalent iodine chemistry. 2 Many chiral hypervalent iodine reagents or catalysts (Figure 1) have been invented by the groups of Wirth, 3 Kita, 4 Ishihara, 5 Fujita, 6 Muñiz, 7 Legault 8 , and others, 9 to effect asymmetric transformations that would be difficult to accomplish otherwise. 2,10…”

Section: Introductionmentioning

confidence: 99%

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Mechanism and Origins of Chemo- and Stereoselectivities of Aryl Iodide-Catalyzed Asymmetric Difluorinations of β-Substituted Styrenes

et al. 2018

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The mechanism of the aryl iodide-catalyzed asymmetric migratory geminal difluorination of β-substituted styrenes (Banik et al. Science 2016, 353, 51) has been explored with density functional theory computations. The computed mechanism consists of (a) activation of iodoarene difluoride (ArIF2), (b) enantiodetermining 1, 2-fluoroiodination, (c) bridging phenonium ion formation via SN2 reductive displacement, and (d) regioselective fluoride addition. According to the computational model, the ArIF2 intermediate is stabilized through halogen-π interactions between the electron-deficient iodine(III) center and the benzylic substituents at the catalyst stereogenic centers. Interactions with the catalyst ester carbonyl groups (I(III)+⋯O) are not observed in the unactivated complex, but do occur upon activation of ArIF2 through hydrogen bonding interactions with external Brønsted acid (HF). The 1, 2-fluoroiodination occurs via alkene complexation to the electrophilic, cationic I(III) center followed by C−F bond formation anti to the forming C−I bond. The bound olefin and the C−I bond of catalyst adopt a spiro-arrangement in the favored transition structures but a nearly periplanar arrangement in the disfavored transition structures. Multiple attractive non-covalent interactions, including slipped π⋯π stacking, C–H⋯O, and C–H⋯π interactions, are found to underlie the high asymmetric induction. The chemoselectivity for 1,1-difluorination versus 1,2-difluorination is controlled mainly by 1) the steric effect of the substituent on the olefinic double bond, and 2) the nucleophilicity of the carbonyl oxygen of substrate.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Mechanism and Origins of Chemo- and Stereoselectivities of Aryl Iodide-Catalyzed Asymmetric Difluorinations of β-Substituted Styrenes

et al. 2018

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“…Hypervalent iodine(III) compounds have been emerged as an efficient reagent in the dehydrogenative C−C bond formations [9] such as cross‐coupling reactions of arenes with different kinds of arenes, [10] aldehydes, [11a] active methines [11b] or simple alkanes, [11c] arylation of alkenes [12a,b] or alkynes, [12c,d] and iodonio‐Claisen rearrangement [13] . Some of these dehydrogenative reactions have been extended to the iodine(III)‐catalysis [14] .…”

Section: Methodsmentioning

confidence: 99%

Dehydrogenative Cycloisomerization/Arylation Sequence ofN‐Propargyl Carboxamides with Arenes by Iodine(III)‐Catalysis

et al. 2022

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Dehydrogenative cycloisomerization/arylation sequence of heteroatom nucleophile‐tethered unactivated alkynes provides a facile and powerful approach to C−C bond formation between the generated heterocycles and unfunctionalized arenes. Here, we describe a hypervalent iodine(III)‐catalyzed synthesis of oxazoles concomitant with the introduction of aryl groups into side chain from N‐propargyl carboxamides and arenes, representing first C(sp3)−C(sp2) bond formation by the catalytic dehydrogenative cycloisomerization/arylation reaction in exo‐dig modes.

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“…Chiral hypervalent iodines have become attractive catalysts and mediators for asymmetric oxidation reactions. 17 − 20 These species have been successfully employed for a wide range of enantioselective C–C, 21 − 23 C–O, 24 − 28 and C–N 29 , 30 bond formation reactions using alkene derivatives as substrates. The groups of Kitamura, 31 Jacobsen, 32 and Gilmour 33 reported pioneering methods for catalytic fluorination of olefins with in situ generated iodine(III) fluorides.…”

Section: Introductionmentioning

confidence: 99%

Enantioselective Construction of Tertiary Fluoride Stereocenters by Organocatalytic Fluorocyclization

et al. 2020

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1,1-Disubstituted styrenes with internal oxygen and nitrogen nucleophiles undergo oxidative fluorocyclization reactions with in situ generated chiral iodine(III)-catalysts. The resulting fluorinated tetrahydrofurans and pyrrolidines contain a tertiary carbon−fluorine stereocenter. Application of a new 1-naphthyllactic acid-based iodine(III)-catalyst allows the control of tertiary carbon− fluorine stereocenters with up to 96% ee. Density functional theory calculations are performed to investigate the details of the mechanism and the factors governing the stereoselectivity of the reaction.

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Metal‐Free Enantioselective Oxidative Arylation of Alkenes: Hypervalent‐Iodine‐Promoted Oxidative C−C Bond Formation

Cited by 10 publications

References 71 publications

Mechanism and Origins of Chemo- and Stereoselectivities of Aryl Iodide-Catalyzed Asymmetric Difluorinations of β-Substituted Styrenes

Mechanism and Origins of Chemo- and Stereoselectivities of Aryl Iodide-Catalyzed Asymmetric Difluorinations of β-Substituted Styrenes

Dehydrogenative Cycloisomerization/Arylation Sequence ofN‐Propargyl Carboxamides with Arenes by Iodine(III)‐Catalysis

Enantioselective Construction of Tertiary Fluoride Stereocenters by Organocatalytic Fluorocyclization

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