The University of Tokyo · 화학
타카후미 야타베 교수의 연구실은 주로 이종화학적 촉매를 활용한 고도로 선택적인 유기합성 반응 개발에 중점을 두고 있습니다. 특히 금속 나노입자(금, palladium, 백금 등)를 지지체로 사용한 고체 촉매를 통해 탄소-수소 결합 활성화, 탈수소화, 알킬화 등 다양한 유기 반응을 효율적으로 진행합니다. 연구는 원자 수준의 촉매 구조 규명과 반응 메커니즘의 기초적 이해를 바탕으로 하며, 자연계의 생합성 경로를 모방하거나 초월하는 새로운 합성 전략을 개발하고자 합니다. 특히 수소 수용체가 필요 없는 탈수소화 반응과 자연계에서 흔하지 않은 고리 구조를 가진 플라보노이드 유도체의 합성에 초첨을 맞추고 있습니다.
표시된 성과는 수집된 데이터 기준으로 산출되며, 일부 차이가 있을 수 있습니다.
Flavones are a class of natural products with diverse biological activities and have frequently been synthesized by step-by-step procedures using stoichiometric amounts of reagents. Herein, a catalytic one-pot procedure for the synthesis of flavone and its derivatives is developed. In the presence of gold nanoparticles supported on a Mg-Al layered double hydroxide (Au/LDH), various kinds of flavones can be synthesized starting from 2'-hydroxyacetophenones and benzaldehydes (or benzyl alcohols).
Flavonoids, which are ubiquitous plant secondary metabolites obtained from chalcones, mostly possess 6-membered C-rings derived from 6-endo-trig cyclization of chalcones. However, aurones, which are a class of flavonoids that rarely occur naturally, possess unusual 5-membered C-rings biosynthesized from chalcones by mainly performing B-ring oxidation. Therefore, the chemical catalytic transformation from simple chalcones into aurones is attractive, because it overcomes the drawback of known limi
By utilizing hydrazine (N<sub>2</sub>H<sub>4</sub>) as the nitrogen source in the presence of a hydroxyapatite-supported Pd nanoparticle catalyst (Pd/HAP), various primary anilines can be selectively synthesized from cyclohexanones via acceptorless dehydrogenative aromatization. The strong nucleophilicity of N<sub>2</sub>H<sub>4</sub> and the stability of the hydrazone intermediates can effectively suppress the formation of the undesired secondary aniline byproducts.
Although catalytic dehydrogenative aromatization from cyclohexanones and NH<sub>3</sub> is an attractive synthetic method for primary anilines, using a hydrogen acceptor was indispensable to achieve satisfactory levels of selectivity in liquid-phase organic synthetic systems without photoirradiation. In this study, we developed a highly selective synthesis of primary anilines from cyclohexanones and NH<sub>3</sub> via efficient acceptorless dehydrogenative aromatization heterogeneously catalyzed
Although hydroacylation is a very useful reaction for producing ketones from aldehydes with 100% atom efficiency, classical Rh-catalyzed hydroacylation presents several problems, including the need for transition metal catalysts, unwanted decarbonylation of aldehydes, and difficulty in regioselectivity control. However, formal hydroacylation utilizing the nucleophilicity of terminal alkynes can avoid these problems. In this work, we have achieved transition-metal-free formal hydroacylation of te
We focused on identifying a catalytic active site structure at the atomic level and elucidating the mechanism at the elementary reaction level of liquid-phase organic reactions with a heterogeneous catalyst. In this study, we experimentally and computationally investigated efficient C-H bond activation for the selective aerobic α,β-dehydrogenation of saturated ketones by using a Pd-Au bimetallic nanoparticle catalyst supported on CeO<sub>2</sub> (Pd/Au/CeO<sub>2</sub>) as a case study. Detailed
Using Cu/ N -oxyl catalysts, a highly efficient aerobic oxidative esterification reaction of ethylene glycol to various oxalic acid diesters in the presence of other aliphatic primary alcohols was realized.
Abstract Flavones are a class of natural products with diverse biological activities and have frequently been synthesized by step‐by‐step procedures using stoichiometric amounts of reagents. Herein, a catalytic one‐pot procedure for the synthesis of flavone and its derivatives is developed. In the presence of gold nanoparticles supported on a Mg‐Al layered double hydroxide (Au/LDH), various kinds of flavones can be synthesized starting from 2′‐hydroxyacetophenones and benzaldehydes (or benzyl al
Regioselective transformations of tertiary amines, which are ubiquitously present in natural products and drugs, are important for the development of novel medicines. In particular, the oxidative α-C-H functionalisation of tertiary amines with nucleophiles via iminium cations is a promising approach because, theoretically, there is almost no limit to the type of amine and functionalisation. However, most of the reports on oxidative α-C-H functionalisations are limited to α-methyl-selective or no
This study rationally designed a heterogeneously catalyzed system (i.e., using Ni-Pd alloy nanoparticles supported on hydroxyapatite (Ni-Pd/HAP) under an H<sub>2</sub> atmosphere) achieving an efficient base-free formal C-S bond metathesis of various thiols via suppression of the Ni catalysis deactivation.
<i>m</i>-Disubstituted arenes are important in various fields but difficult to be directly synthesized by classical methods in the case of two electron-donating substituents due to the <i>o</i>,<i>p</i>-orientation. Dehydrogenative aromatization from nonaromatic cyclohexenone motifs and nucleophiles via 1,2- and 1,4-addition to produce <i>m</i>-disubstituted arenes is promising as the novel process overcoming the intrinsic problems derived from using aromatic compounds as the substrates; however
Here, an undirected acceptorless dehydrogenative silylation of benzylic C(sp 3 )–H bonds was developed using a CeO 2 -supported highly dispersed Ni(0) nanocatalyst.
Azobenzenes have been ubiquitously utilized and synthesized in well-established methods represented as azo coupling for a long time; however, all the available azobenzene synthesis strategies use aromatic compounds as substrates, which inherently limit the regioselectivity of substituents because of ortho/meta/para-orientation and frequently require multistep procedures. Dehydrogenative aromatization from cyclohexanones, which can be regioselectively functionalized using classical methods withou