大阪大学 · Materials Science
마코토 ヤ수다 교수의 연구실은 인화합물, 특히 InCl₃를 촉매로 사용하는 고유한 유기합성 반응을 중심으로 연구를 전개하고 있습니다. 알코올의 직접 알킬화, 환원, 할로젠화 등의 반응에서 부산물이 수소이온과 물뿐인 ‘염기 없이, 염기 없이’ 반응을 유도하는 친환경적이고 고순도의 제품 수확이 가능합니다. 특히 산화환원 반응에서의 선택성과 산화감수성 기능기를 가진 화합물에도 적용 가능한 고도의 반응성 제어 능력이 두드러집니다.
표시된 성과는 수집된 데이터 기준으로 산출되며, 일부 차이가 있을 수 있습니다.
The unsalted variety: The direct coupling reaction of alcohols with active methylenes, alkoxyketones, or indoles catalyzed by InCl3 proceeds without the formation of metal salts (see scheme). As H2O is the only by-product of this system, the alkylated products are easily isolated in pure form, and the reaction is suitable for large-scale synthesis. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2006/z503263_s.pdf or from the author.
The direct reduction of alcohols using chlorodiphenylsilane as a hydride source in the presence of a catalytic amount of indium trichloride is described. Benzylic alcohols, secondary alcohols, and tertiary alcohols were effectively reduced to give the corresponding alkanes in high yields. A compound bearing both primary and secondary hydroxyl groups was reduced only at the secondary site to afford the primary alcohol after workup with Bu(4)NF. This system showed high chemoselectivity only for th
Straightforward substitution: An excellent combination of a silyl nucleophile and indium catalyst was used to accomplish the dehydroxylation/alkylation of alcohols under nearly neutral conditions (see scheme, Si=silyl group) even though this type of reaction usually requires at least an equimolar amount of acid. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2004/z53121_s.pdf or from the author. Please note: The publisher is not res
The InCl3-catalyzed reaction of alcohols with chlorodimethylsilane (HSiMe2Cl) in the presence of benzil gave the corresponding organic chlorides under mild conditions. Benzil significantly changes the reaction course because the reducing product through dehydroxyhydration was obtained in the absence of benzil. The secondary or tertiary alcohols were effectively chlorinated. The substrates bearing acid-sensitive functional groups were also applied to this system. The highly selective chlorination
The reaction of tin enolates 1 with alpha-chloro- or bromoketones 2 gave gamma-diketones (1,4-diketones) 3 catalyzed by zinc halides. In contrast to the exclusive formation of 1,4-diketones 3 under catalytic conditions, uncatalyzed reaction of 1 with 2 gave aldol-type products 4 through carbonyl attack. NMR study indicates that the catalyzed reaction includes precondensation between tin enolates and alpha-haloketones providing an aldol-type species and their rearrangement of the oxoalkyl group w
Ohne Salz, bitte! Bei der direkten Kupplung von Alkoholen mit aktivierten Methylenen, Alkoxyketonen und Indolen unter InCl3-Katalyse fallen keine Metallsalze, sondern lediglich H2O als Beiprodukt an (siehe Schema). Daher sind die alkylierten Produkte leicht isolierbar, und das System eignet sich für Synthesen im großen Maßstab. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2001/2006/z503263_s.pdf or from the author. Please note: The pub
Abstract In cultures of rat cortical neurons, we found that stimulation of tyrosine receptor kinase B (TrkB) with brain‐derived neurotrophic factor (BDNF) induced a biphasic expression of BDNF exon IV–IX mRNA, which became obvious 1–3 h (primary induction) and 24–72 h (delayed induction) after the stimulation, and characterized the delayed induction in relation to the mRNA expression of activity‐regulated cytoskeleton‐associated protein (Arc). Withdrawal of BDNF from the medium after stimulation
The diastereoselective addition of gamma-substituted allylic nucleophiles to ketones has been accomplished to give tertiary homoallylic alcohols. The reaction of tributylcinnamyltin 1a with simple ketones 2 in the presence of stannous chloride (SnCl(2)) gave the tertiary homoallylic alcohols 3, which include the anti form (based on Ph and OH), with high diastereoselectivity. In the reaction course, transmetalation of tributylcinnamyltin 1a with SnCl(2) proceeds to form an active nucleophile whic
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTNMR Studies of Five-Coordinate Tin Enolate: An Efficient Reagent for Halo Selective Reaction toward .alpha.-Halo Ketone or .alpha.-Halo ImineMakoto Yasuda, Yasuhiro Katoh, Ikuya Shibata, Akio Baba, Haruo Matsuda, and Noboru SonodaCite this: J. Org. Chem. 1994, 59, 16, 4386–4392Publication Date (Print):August 1, 1994Publication History Published online1 May 2002Published inissue 1 August 1994https://doi.org/10.1021/jo00095a011RIGHTS & PERMISSIONSArticle
Sei nicht sauer! Ein Silylnucleophil kombiniert mit einem Indiumkatalysator wurde zur Dehydroxylierung/Alkylierung von Alkoholen unter fast neutralen Bedingungen eingesetzt (siehe Schema). Üblicherweise erfordert dieser Reaktionstyp äquimolare Mengen an Säure.
