Transition metal-mediated oxidations utilizing monomeric iodosyl- and iodylarene species

Yusubov, Mekhman S.; Nemykin, Victor N.; Zhdankin, Viktor V.

doi:10.1016/j.tet.2010.04.046

Cited by 83 publications

(49 citation statements)

References 97 publications

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“…When chiral phosphine ligands including DIOP (L1), SEGphos (L2), and PHOX( L3)w ere utilized, no desired reaction occurred (entries 1-3). [10] Thes ubsequent mCPBA-mediated Baeyer-Villiger oxidation led to an efficient synthesis of achiral chromanone (5). In all the above-mentioned cases, recovery of 1a and formation of some by-products (3a-1-4) were observed.…”

Section: Youxiang Jin and Chuan Wang*mentioning

confidence: 95%

Nickel‐Catalyzed Asymmetric Reductive Arylalkylation of Unactivated Alkenes

2019

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Reported is an asymmetric reductive dicarbofunctionalization of unactivated alkenes.U nder the catalysis of aN i/BOXs ystem, various aryl bromides,i ncorporating ap endant olefinic unit, were successfully reacted with an arrayo fp rimary alkylb romides in the presence of Zn as ar eductant, furnishing as eries of benzene-fused cyclic compounds bearing aquaternary stereocenter in high enantioselectivities.N otably,t his reaction avoids the use of pregenerated organometallics and demonstrates high tolerance of sensitive functionalities.T he preliminary mechanistic investigations reveal that this Ni-catalyzed reaction proceeds as acascade consisting of migratory insertion and cross-coupling with an ickel(I)-mediated intramolecular 5-exo cyclization as the enantiodetermining step.Asymmetric difunctionalizations of unactivated alkenes are among the most important reactions in organic synthesis,a s diverse optically active compounds can be accessed in asingle step using simple olefins as precursors.T ransition-metal catalysis has proven to be ap owerful tool for dicarbofunctionalizations of unactivated alkenes including diarylation, dialkylation as well as arylalkylation, and tremendous advances have been achieved recently using both redox-neutral [1][2][3] and reductive strategies. [4] However,a symmetric versions of these reactions are still rare.I nt he field of diarylation, Sigman et al. developed aP d-catalyzed enantioselective diphenylation of 1,3-dienes, [3c] while Brown and his coworker reported aC u-promoted asymmetric diarylation of pendant olefins tethered on aryl boronates. [2d] Recently,L iu et al. achieved Cu-catalyzed enantioselective dicarbofuntionalizations of styrenes involving the installation of aC F 3 moeity. [3d,j] Furthermore,F ue tal. accomplished an enantioselective variant of the two-component arylalkylation. [2b] In this Ni-catalyzed reaction, arylboranes incorporating aterminal olefinic unit were reacted with unactivated alkyl halides, affording various benzofurans and indanes in high enantioselectivities (Scheme 1A). However,a ll the aforementioned asymmetric dicarbofunctionalizations of unactivated olefins require the use of pregenerated organometallics as coupling partners,and is less desirable from the viewpoint of both stepeconomy and functionality tolerance.On the contrary,t he reductive strategy of dicarbofunctionalizations of C À Cd ouble bonds allows the incorporation of two carbo moieties directly from either aryl or alkyl halides with the assistance of ar educing agent, and thus eliminates the additional step of preparation of sensitive organometallics,a sw ell as the related issue of functional-group compatibility.D espite rapid progresses in this area, the asymmetric version of reductive dicarbofunctionalization of unactivated olefins still remains elusive. [5,6] Very recently,o ur group reported ar acemic version of Ni-catalyzed reductive arylalkylation of unactivated alkenes tethered to aryl bromides. [4i] In this context, we report asignificant advance of our method as w...

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Section: Youxiang Jin and Chuan Wang*mentioning

confidence: 95%

Nickel‐Catalyzed Asymmetric Reductive Arylalkylation of Unactivated Alkenes

2019

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“…On the basis of the ESI−MS study of the reactions of ArI with Oxone, 10 we assume that the initial oxidation of 2-iodobiphenyl 6 affords iodine(III) intermediate 12, which cyclizes to dibenziodolium sulfate 13 upon subsequent treatment with concentrated sulfuric acid. The final product 13 is isolated in high yield as a pale yellow crystalline solid by filtration of the reaction mixture after addition of ice-cold water.…”

Section: The Journal Of Organic Chemistrymentioning

confidence: 99%

Preparation and X-ray Structural Study of Dibenziodolium Derivatives

et al. 2015

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New experimental procedures for the preparation of dibenziodolium salts by oxidative cyclization of 2-iodobiphenyl in the presence of appropriate strong acids are described. Particularly useful is a convenient one-pot synthesis of dibenziodolium hydrogen sulfate from 2-iodobiphenyl using Oxone as an inexpensive and environmentally safe oxidant. Dibenziodolium hydrogen sulfate, bis(triflyl)imidate, or triflate can be readily converted to various other dibenziodolium derivatives (chloride, bromide, thiocyanate, azide, cyanide, phenylsulfinate) by anion exchange. Structures of key products have been established by single-crystal X-ray diffraction analysis. Particularly interesting is the X-ray structure of dibenziodolium thiocyanate, which represents the first example of a structurally characterized hypervalent iodine compound with a relatively short iodine-sulfur secondary bond distance.

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“…[1][2][3] These are most commonly iron [4][5][6][7] and manganese [8][9][10][11] porphyrin, Mn-corrole, [12] Mn-corrolazinato, [13,14] and Mn-salen complexes, [15] and even cytochrome P450. [1][2][3] These are most commonly iron [4][5][6][7] and manganese [8][9][10][11] porphyrin, Mn-corrole, [12] Mn-corrolazinato, [13,14] and Mn-salen complexes, [15] and even cytochrome P450.…”

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An Iron(III) Iodosylbenzene Complex: A Masked Non‐Heme Fe^VO

2012

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Iodosylarenes are an important class of oxygen atom transfer reagents in organic synthesis, and they are often used in conjunction with transition-metal-based catalysts. [1][2][3] These are most commonly iron [4][5][6][7] and manganese [8][9][10][11] porphyrin, Mn-corrole, [12] Mn-corrolazinato, [13,14] and Mn-salen complexes, [15] and even cytochrome P450. [16] Hypervalent metaloxo complexes that relay the oxygen atom from the iodosylarene donor to the substrate acceptor are most commonly invoked as the active oxidants in these catalytic mechanisms. Accordingly iodsosylarenes have been used in the preparation of hypervalent metal-oxo complexes. No metal-complexed iodosylarene has been structurally characterized in the solid state; however, the isolation of a reactive iodosylbenzene complex of Mn-porphyrin was reported nearly 30 years ago. [17] Oxygen atom transfer from iodosylarenes to LM n+ complexes give the corresponding LM (n+2)+ O species (or LC + M (n+1)+ O if the ligand is non-innocent, for example when L = porphyrin) [Equation (1), steps i + ii]. Occasionally, intervening transient species assigned to metal-iodosylarene adducts have been spectroscopically identified in these types of reactions. More or less unstable Mn V O porphyrin [8] and salen [13,18,19] systems, Cr V O, [20] [(porphC)Fe IV O] +[6, 7] systems, and [Fe IV O(tmc)] 2+[21] (tmc = tetramethylcyclam) have been accessed by oxygen atom transfer from iodosylbenzene to the appropriate Mn III , Cr III , Fe III , and Fe II precursors respectively. Recently, a novel Co IV O solution species was generated at À60 8C by the reaction of 2-(tert-butylsulfonyl)iodosylbenzene with [Co II (TMG 3 tren)(OTf)] + . [22] Nam et al. have demonstrated the back-reaction of the equilibrium ii in Equation (1) by formation of a spectrosopically detected species assigned to [(porph)Fe III (OIPh)] + from the reaction of [(porphC)Fe IV O] + with iodobenzene. [6]By using the monoanionic hexadentate ligand N,N,N'tris(2-pyridylmethyl)ethylendiamine-N'-acetate (tpena À ), we describe herein the structural characterization of a reactive high-spin seven-coordinate iron(III) complex, [(tpena)Fe-(OIC 6 H 5 )] 2+ (1), which contains an auxiliary iodosylbenzene ligand. Complex 1 is prepared by dissolving the oxo-bridged complex [(tpenaH)Fe(m-O)Fe(tpenaH)] 4+ (2) in acetonitrile to form [Fe III (tpena)] 2+ (3) [Equation (2)], which then reacts with iodosylbenzene to give 1 [Equation (3)]. Dehydration and oxo bridge cleavage of 2 seems particularly facilitated by tpena À by comparison to most other oxo-bridged diiron(III) species, which are typically more robust in solution. [23,24] The uncoordinated basic pyridyl groups may be playing an active role in this process. If protonated, as is found in the crystal structure (see below), a dehydration reaction is formally intramolecular. Thus solutions of 2 turn red within minutes owing to the formation of 3, which has been characterized by ESI-MS, UV/Vis, and ESR spectroscopy. [25] The crystal structure of the Co III analogue of 3 is ...

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Transition metal-mediated oxidations utilizing monomeric iodosyl- and iodylarene species

Cited by 83 publications

References 97 publications

Nickel‐Catalyzed Asymmetric Reductive Arylalkylation of Unactivated Alkenes

Nickel‐Catalyzed Asymmetric Reductive Arylalkylation of Unactivated Alkenes

Preparation and X-ray Structural Study of Dibenziodolium Derivatives

An Iron(III) Iodosylbenzene Complex: A Masked Non‐Heme Fe^VO

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Transition metal-mediated oxidations utilizing monomeric iodosyl- and iodylarene species

Cited by 83 publications

References 97 publications

Nickel‐Catalyzed Asymmetric Reductive Arylalkylation of Unactivated Alkenes

Nickel‐Catalyzed Asymmetric Reductive Arylalkylation of Unactivated Alkenes

Preparation and X-ray Structural Study of Dibenziodolium Derivatives

An Iron(III) Iodosylbenzene Complex: A Masked Non‐Heme FeVO

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An Iron(III) Iodosylbenzene Complex: A Masked Non‐Heme Fe^VO