金(I)-催化1,1-二氟烯与醛的[2 + 2]和[3 + 2]环加成：氟化氧烷和呋喃的可切换合成

IF 5 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Letters Pub Date : 2025-01-18 DOI:10.1021/acs.orglett.4c04185

Daisuke Miyazaki, Konami Kudo, Yusuke Fujiki, Natsumi Watanabe, Toru Matsui, Junji Ichikawa, Kohei Fuchibe

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引用次数: 0

摘要

在Au(I)催化剂的作用下，1,1-二氟烯与醛进行了区域选择性[2 + 2]和[3 + 2]环加成反应。AuCl催化剂使1,1-二氟烯发生α，β-选择性[2 + 2]环加成反应，生成(E)-3-烷基烯-2,2-二氟烷。相反，AuCl(IPr) -AgSbF6催化剂促进α，γ-选择性[3 + 2]环加成，然后脱氢氟化生成芳构化的2-氟呋喃。DFT计算（B3LYP水平）表明，前一种反应是通过含Au（III）的金属环进行的，而后一种反应是通过环Au(I)类碳环进行的。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Gold(I)-Catalyzed [2 + 2] and [3 + 2] Cycloadditions of 1,1-Difluoroallenes with Aldehydes: Switchable Syntheses of Fluorinated Oxetanes and Furans

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Gold(I)-Catalyzed [2 + 2] and [3 + 2] Cycloadditions of 1,1-Difluoroallenes with Aldehydes: Switchable Syntheses of Fluorinated Oxetanes and Furans

1,1-Difluoroallenes underwent regioselective [2 + 2] and [3 + 2] cycloadditions with aldehydes using Au(I) catalysts. An AuCl catalyst enabled an α,β-selective [2 + 2] cycloaddition of 1,1-difluoroallenes, yielding (E)-3-alkylidene-2,2-difluorooxetanes. Conversely, an AuCl(IPr)–AgSbF₆ catalyst facilitated an α,γ-selective [3 + 2] cycloaddition, followed by dehydrofluorination to produce aromatized 2-fluorofurans. DFT calculations (B3LYP level) suggested that the former reaction proceeded through Au(III)-containing metallacycles, while the latter involved cyclic Au(I) carbenoids.

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来源期刊

Organic Letters 化学-有机化学

CiteScore

9.30

自引率

11.50%

发文量

1607

审稿时长

1.5 months

期刊介绍： Organic Letters invites original reports of fundamental research in all branches of the theory and practice of organic, physical organic, organometallic,medicinal, and bioorganic chemistry. Organic Letters provides rapid disclosure of the key elements of significant studies that are of interest to a large portion of the organic community. In selecting manuscripts for publication, the Editors place emphasis on the originality, quality and wide interest of the work. Authors should provide enough background information to place the new disclosure in context and to justify the rapid publication format. Back-to-back Letters will be considered. Full details should be reserved for an Article, which should appear in due course.