Thangarasu Arun K, Yadhukrishnan Velickakathu O, Krishnakumar K A, Varma Sanjay Suresh, Lankalapalli Ravi S
Chemical Sciences and Technology Division, CSIR-National Institute for Interdisciplinary Science and Technology, Thiruvananthapuram 695019, India.
Academy of Scientific & Innovative Research (AcSIR), Ghaziabad-201002, India.
ACS Org Inorg Au. 2021 Aug 20;2(1):3-7. doi: 10.1021/acsorginorgau.1c00015. eCollection 2022 Feb 2.
The limitation of the CuAAC "click" reaction with a 2-azidopyridine substrate, owing to its equilibrium with a tetrazole isomer, is exploited herein for its utility in the Glaser-Hay reaction. A catalytic combination of a 2-azidopyridine analogue, 4-azido-5-pyrrolo[3,2-]pyrimidine, and CuI afforded homocoupled products of terminal alkynes, without any trace of triazole product, under mild conditions with a broad substrate scope. Emphasis on carbohydrate-based substrates appended to a propargylic group led to 1,3-diynes in good to excellent yields.
由于2-叠氮基吡啶底物与四唑异构体存在平衡，铜催化的叠氮化物-炔烃环加成（CuAAC）“点击”反应存在局限性，本文利用该局限性将其应用于格拉泽-海反应。在温和条件下，2-叠氮基吡啶类似物4-叠氮基-5-吡咯并[3,2-]嘧啶与碘化亚铜的催化组合，能使末端炔烃发生均偶联反应生成产物，且无任何三唑产物痕迹，底物范围广泛。对连接在炔丙基上的碳水化合物基底物的研究表明，能以良好至优异的产率得到1,3-二炔。
