- Substrate-Controlled Chemo-/Enantioselective Synthesis of α-Benzylated Enals and Chiral Cyclopropane-Fused 2-Chromanone Derivatives
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Substrate-controlled cascade reactions between α,β-unsaturated aldehydes or their analogues and 2,4-dinitrobenzyl chloride in the presence of a chiral secondary amine as the catalyst and base were developed, to obtain a broad spectrum of α-benzylated enals and enantioenriched cyclopropane-fused chroman-2-one derivatives. The cyclopropane-tethered iminium ion clearly served as a key intermediate in these reactions to trigger stereochemical outcomes, one of which was supported by a control experiment. (Figure presented.).
- Byeon, Huimyoung,Ryu, Sunghyeon,Yoo, Eun Jeong,Yang, Jung Woon
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supporting information
p. 5085 - 5091
(2021/09/20)
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- Palladium/Copper-catalyzed Oxidation of Aliphatic Terminal Alkenes to Aldehydes Assisted by p-Benzoquinone
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The development of an anti-Markovnikov Wacker-type oxidation for simple aliphatic alkenes is a significant challenge. Herein, a variety of aldehydes can be selectively obtained from various unbiased aliphatic terminal alkenes using PdCl2(MeCN)2/CuCl in the presence of p-benzoquinone (BQ) under mild reaction conditions. Isomerization of the terminal alkene to the internal alkene was suppressed via slow addition of the starting material to the reaction mixture. In addition to the Pd catalyst, CuCl and BQ were essential in order to obtain the anti-Markovnikov product with high selectivity. Terminal alkenes bearing a halogen substituent afforded their corresponding aldehydes with high anti-Markovnikov selectivity. The halogen acts as a directing group in the reaction. DFT calculations indicate that a μ-chloro Pd(II)?Cu(I) bimetallic species with BQ coordinated to Cu is the catalytically active species in the case of a terminal alkene without a directing group.
- Komori, Saki,Yamaguchi, Yoshiko,Murakami, Yuka,Kataoka, Yasutaka,Ura, Yasuyuki
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p. 3946 - 3955
(2020/07/06)
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- Merging visible light photocatalysis of dye-sensitized TiO2 with TEMPO: The selective aerobic oxidation of alcohols
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The selective oxidation of alcohols to aldehydes or ketones is very difficult to accomplish when the oxidant is molecular oxygen (O2) and the reaction is carried out under ambient conditions. To meet these challenges, visible light photocatalysis was exploited to enable the use of O2 for the selective oxidation of alcohols at room temperature. In this scheme, eosin Y, an organic dye, was connected with TiO2 to capture visible light, leading to consequential photocatalytic processes. More importantly, these photocatalytic processes can be neatly merged with the redox catalytic cycles of TEMPO, which in turn induce the oxidation of alcohols under visible light irradiation. This work suggests that the merger of visible light photocatalysis and TEMPO catalysis has great potential for execution of challenging oxidative transformations.
- Zhang, Yichi,Wang, Zhan,Lang, Xianjun
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p. 4955 - 4963
(2017/11/09)
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