Asymmetric Hydrogenation of Heteroarenes and Arenes

Wang, Duo‐Sheng; Chen, Qing‐An; Lü, Shouqin; Zhou, Yong‐Gui

doi:10.1021/cr200328h

Cited by 981 publications

(350 citation statements)

References 161 publications

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“…It is promising that this dehydroxylation could be used to provide aimed anthracycline analogs in the future by protein engineering. In addition, dearomatizations are chemically challenging in a sense both of chemistry and of biology (16,17,27), as the asymmetric hydrogenation of aromatic compounds, which was considered a versatile and practical synthetic strategy method to obtain chiral compound, has been an active and attractive field of methodology research (28,29). Recently, characterization of the NADPH-dependent reductases involved in fungal 1,8-dihydroxynaphthalene melanin, monodictyphenone, and aflatoxin B1 biosynthesis expanded the substrates to hydroxynaphthoquinones and tricyclic anthrahydroquinones (30)(31)(32)(33).…”

Section: Discussionmentioning

confidence: 99%

Hydroxyl regioisomerization of anthracycline catalyzed by a four-enzyme cascade

Zhang

Gong

Zhou

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

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Ranking among the most effective anticancer drugs, anthracyclines represent an important family of aromatic polyketides generated by type II polyketide synthases (PKSs). After formation of polyketide cores, the post-PKS tailoring modifications endow the scaffold with various structural diversities and biological activities. Here we demonstrate an unprecedented four-enzyme-participated hydroxyl regioisomerization process involved in the biosynthesis of kosinostatin. First, KstA15 and KstA16 function together to catalyze a cryptic hydroxylation of the 4-hydroxyl-anthraquinone core, yielding a 1,4-dihydroxyl product, which undergoes a chemically challenging asymmetric reduction-dearomatization subsequently acted by KstA11; then, KstA10 catalyzes a region-specific reduction concomitant with dehydration to afford the 1-hydroxyl anthraquinone. Remarkably, the shunt product identifications of both hydroxylation and reduction-dehydration reactions, the crystal structure of KstA11 with bound substrate and cofactor, and isotope incorporation experiments reveal mechanistic insights into the redox dearomatization and rearomatization steps. These findings provide a distinguished tailoring paradigm for type II PKS engineering.biosynthesis | C-4 deoxyanthracycline | two-component hydroxylase | NmrA-like short-chain dehydrogenase | dehydroxylation

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Section: Discussionmentioning

confidence: 99%

Hydroxyl regioisomerization of anthracycline catalyzed by a four-enzyme cascade

Zhang

Gong

Zhou

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

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“…[76] Asymmetric hydrogenation of heteroaromatic or cyclic unsaturated compounds provides a convenient way for the synthesis of optically active cyclic compounds. [77] In 2013, Ma and Zhou collaboratively studied the catalytic asymmetric hydrogenation of compounds 62 on the basis of their common research interests. Compounds 62 form a class of cyclic ketimines that have a CF 3 group at the unsaturated carbon site; these compounds should be interesting candidates as starting materials for the formation of the corresponding hydrogenated adducts of CF 3 -dihydroquinazolinones in a highly atom-economic fashion.…”

Section: Chiral Trifluoromethylated Dihydroquinazolinones (Cf 3 -Dihymentioning

confidence: 99%

Catalytic Asymmetric Synthesis of Enantioenriched Heterocycles Bearing a CCF₃ Stereogenic Center

Huang

Yang

Chen

et al. 2015

Chemistry A European J

132

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Given the important agricultural and medicinal application of optically pure heterocycles bearing a trifluoromethyl group at the stereogenic carbon center in the heterocyclic framework, the exploration of efficient and practical synthetic strategies to such types of molecules remains highly desirable. Catalytic enantioselective synthesis has one clear advantage that it is more cost-effective than other synthetic methods, but remains limited by challenges in achieving excellent yield and stereoselectivities with a low catalyst loading. Thus far, numerous models of organo- and organometal-catalyzed asymmetric reactions have been exploited to achieve this elusive goal over the past decade. This review article describes recent progress on this research topic, and focuses on an understanding of the catalytic asymmetric protocols exemplified in the catalytic enantioselective synthesis of a wide range of complex enantioenriched trifluoromethylated heterocycles.

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“…This method was also applicable to the hydrogenation of more challenging difluoro substituted substrates (69-86% ee). The protecting group (PMP) on the products could be readily removed through oxidative cleavage with Ce(NH 4 ) 2 (NO 3 ) 6 (CAN) giving chiral b-fluorinated primary amines. By introducing the strong electron-withdrawing group on the nitrogen atom, palladium catalyzed asymmetric hydrogenation could be extended to nonfluorinated imines.…”

Section: Qing-an Chenmentioning

confidence: 99%

Homogeneous palladium-catalyzed asymmetric hydrogenation

et al. 2013

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The transition metal catalyzed asymmetric hydrogenation of unsaturated compounds arguably presents one of the most attractive methods for the synthesis of chiral compounds. Over the last few decades, Pd has gradually grown up as a new and popular metal catalyst in homogeneous asymmetric hydrogenation the same as traditional Ru, Rh and Ir catalysts. Much progress has been successfully achieved in the asymmetric reduction of imines, enamines, olefins, ketones and heteroarenes. It was also found that palladium catalyzed asymmetric hydrogenation could be used as a key step in tandem reactions to quickly synthesize chiral compounds. This tutorial review intends to offer an overview of recent progress in homogeneous palladium catalyzed asymmetric hydrogenation and should serve as an inspiration for further advances in this area. Key learning points(1) The general mechanism for homogeneous palladium catalyzed asymmetric hydrogenation.(2) The palladium catalysts' tolerance against acid, water and air in the hydrogenation process.(3) The substrate scopes and limitations in these transformations. (4) The common hydrogen sources used in these catalytic systems.(5) The general solvent-dependent phenomena in these transformations.

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Asymmetric Hydrogenation of Heteroarenes and Arenes

Cited by 981 publications

References 161 publications

Hydroxyl regioisomerization of anthracycline catalyzed by a four-enzyme cascade

Hydroxyl regioisomerization of anthracycline catalyzed by a four-enzyme cascade

Catalytic Asymmetric Synthesis of Enantioenriched Heterocycles Bearing a CCF₃ Stereogenic Center

Homogeneous palladium-catalyzed asymmetric hydrogenation

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Asymmetric Hydrogenation of Heteroarenes and Arenes

Cited by 981 publications

References 161 publications

Hydroxyl regioisomerization of anthracycline catalyzed by a four-enzyme cascade

Hydroxyl regioisomerization of anthracycline catalyzed by a four-enzyme cascade

Catalytic Asymmetric Synthesis of Enantioenriched Heterocycles Bearing a CCF3 Stereogenic Center

Homogeneous palladium-catalyzed asymmetric hydrogenation

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Product

Resources

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Catalytic Asymmetric Synthesis of Enantioenriched Heterocycles Bearing a CCF₃ Stereogenic Center