A Chiral Hypervalent Iodine(III) Reagent for Enantioselective Dearomatization of Phenols

Dohi, Tomotaka; Maruyama, Akinobu; Takenaga, Naoko; Senami, Kento; Minamitsuji, Yutaka; Fujioka, Hiromichi; Caemmerer, Simon B.; Kita, Yasuyuki

doi:10.1002/ange.200800464

Cited by 149 publications

(57 citation statements)

References 54 publications

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“…[22] Also, it is noteworthy that many organocatalytic oxidative transformations of phenols to cyclohexadienones using various oxidants, such as m-chloroperbenzoic acid and oxone, in the presence of hypervalent iodine catalysts, such as phenyliodine(III) bis(trifluoroacetate), have recently been explored, [23] in addition to the other methods including oxidation with singlet oxygen. [24] The resulting 4-(tert-butylperoxy)cyclohexadienones 2 are versatile synthetic intermediates for C-C bond formation through both Diels-Alder and Michael reactions.…”

Section: Introductionmentioning

confidence: 99%

Ruthenium‐Catalyzed Oxidative Dearomatization of Phenols to 4‐(tert‐Butylperoxy)cyclohexadienones: Synthesis of 2‐Substituted Quinones from p‐Substituted Phenols

et al. 2011

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The ruthenium-catalyzed oxidation of phenols with tert-butyl hydroperoxide efficiently gives the corresponding 4-(tert-butylperoxy)cyclohexadienones. The oxidation proceeds selectively because of ruthenium's ability for rapid single-electron transfer. This biomimetic oxidation reaction is highly useful to obtain the metabolic compounds desired for confirming the safety of medicines and related compounds. Typically, the first metabolic compound of the female hormone estrone is readily obtained by this biomimetic oxidation reaction. The resulting 4-(tert-butylperoxy)cyclohexadienones are versatile synthetic intermediates, which can be transformed into

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Section: Introductionmentioning

confidence: 99%

Ruthenium‐Catalyzed Oxidative Dearomatization of Phenols to 4‐(tert‐Butylperoxy)cyclohexadienones: Synthesis of 2‐Substituted Quinones from p‐Substituted Phenols

et al. 2011

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“…[20][21][22][23][24][25] A breakthrough in the design of a chiral reagent for high stereoselectivity came with the arrival of conformationally rigid 1,1-spiroindanone reagents [22,25d] and conformationally flexible lactate-based reagents. [20][21][22][23][24][25] A breakthrough in the design of a chiral reagent for high stereoselectivity came with the arrival of conformationally rigid 1,1-spiroindanone reagents [22,25d] and conformationally flexible lactate-based reagents.…”

Section: Introductionmentioning

confidence: 99%

Enantioselective Oxidation of Alkenylbenzoates Catalyzed by Chiral Hypervalent Iodine(III) To Yield 4‐Hydroxyisochroman‐1‐ones

2013

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In this study, the enantioselective oxylactonization of ortho‐alk‐1‐enylbenzoates with chiral hypervalent iodine(III) reagents yielded 3‐alkyl‐4‐hydroxyisochroman‐1‐ones with high enantiomeric purity (ca. 90 % ee). The enantioselective oxidation was also performed under catalytic conditions, in which a catalytic amount (10 mol‐%) of a chiral iodoarene was oxidized to the hypervalent iodine species in situ using a stoichiometric co‐oxidant, m‐chloroperbenzoic acid (mCPBA). The catalytic oxidation mediated by chiral hypervalent iodine(III) species yielded enantiocontrolled syn products, while the direct oxidation of the substrate with mCPBA occurred as background oxidation to give racemic anti products. Under optimized conditions, the catalytic oxylactonization led to high levels of enantioselectivity (ca. 90 % ee) and improved syn/anti selectivities (ca. 80 % syn). The product distribution indicated that the lactate side‐chain on the chiral iodoarene precatalyst plays an important role in enhancing both the enantioselectivity and the catalytic efficiency in the oxylactonization.

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“…In 2008, Kita et al [12] reported a creative work on enantioselective synthesis of spirolactone 12a through enantioselective dearomatization reaction of naphthol 11a (R = Br) using a chiral hypervalent iodine(III) reagent 13a bearing conformationally rigid 1,1′-spirobiindane backbone (Scheme 5). Following this work, they reported catalytic version of this reaction as well.…”

Section: Intramolecular Cyclization Reactions Of Carboxylic Acid Derimentioning

confidence: 99%

Green and Catalytic Methods for γ-Lactone Synthesis

Yanai

2015

Green Synthetic Approaches for Biologically Relevant Heterocycles

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A Chiral Hypervalent Iodine(III) Reagent for Enantioselective Dearomatization of Phenols

Cited by 149 publications

References 54 publications

Ruthenium‐Catalyzed Oxidative Dearomatization of Phenols to 4‐(tert‐Butylperoxy)cyclohexadienones: Synthesis of 2‐Substituted Quinones from p‐Substituted Phenols

Ruthenium‐Catalyzed Oxidative Dearomatization of Phenols to 4‐(tert‐Butylperoxy)cyclohexadienones: Synthesis of 2‐Substituted Quinones from p‐Substituted Phenols

Enantioselective Oxidation of Alkenylbenzoates Catalyzed by Chiral Hypervalent Iodine(III) To Yield 4‐Hydroxyisochroman‐1‐ones

Green and Catalytic Methods for γ-Lactone Synthesis

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