Synthesis with Perfect Atom Economy: Generation of Furan Derivatives by 1,3-Dipolar Cycloaddition of Acetylenedicarboxylates at Cyclooctynes

Molecules

Klaus Banert¹  Sandra Bochmann¹  Andreas Ihle¹  Oliver Plefka¹  Florian Taubert¹  Tina Walther¹  Marcus Korb²  Tobias R󼿾r² 

[1] Organic Chemistry, Technische Universität Chemnitz, Strasse der Nationen 62, 09111 Chemnitz, Germany; E-Mails:;Inorganic Chemistry, Technische Universität Chemnitz, 09107 Chemnitz, Germany; E-Mails:

关键词: cascade reactions;    cyclopropenes;    Diels–Alder reactions;    dipolar intermediates;    epoxides;    orthoesters;    oxygen heterocycles;    reaction mechanisms;    retro-Brook reactions;    strained compounds;   

DOI  :  10.3390/molecules190914022

来源: mdpi

【 摘 要 】

Cyclooctyne and cycloocten-5-yne undergo, at room temperature, a 1,3-dipolar cycloaddition with dialkyl acetylenedicarboxylates 1a,b to generate furan-derived short-lived intermediates 2, which can be trapped by two additional equivalents of 1a,b or alternatively by methanol, phenol, water or aldehydes to yield polycyclic products 3b–d, orthoesters 4a–c, ketones 5 or epoxides 6a,b, respectively. Treatment of bis(trimethylsilyl) acetylenedicarboxylate (1c) with cyclooctyne leads to the ketone 7 via retro-Brook rearrangement of the dipolar intermediate 2c. In all cases, the products are formed with perfect atom economy.

【 授权许可】

CC BY   
© 2014 by the authors; licensee MDPI, Basel, Switzerland.