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The computed reaction route consists of: (a) formation of dicopper intermediates, including C\u2212H activation of terminal alkyne, 3+2 ring cycloaddition and ring\u2010reducing reaction and transmetalation, (b) interrupted CuAAC reaction, including di\u2010copper catalyzed ring\u2010opening of 2H\u2010azirines and C\u2212C bond formation to generate the copper\u2010triazoles and \u2010ketenimines, (c) two\u2010step C\u2212N cross\u2010coupling and following (d) multi\u2010step hydrogen transfer by the hydrogen bonding chain of water to promote the C\u2212N formation and another C\u2212N cleavage through the removal of p\u2010tolyl sulfonamides. Our DFT results indicate that the multi\u2010step hydrogen transfer process is the rate\u2010determining step along the potential energy surface profile. The explicit water model was used for systematic determination of barrier for C\u2212C cross\u2010coupling, C\u2212N bond formation and cleavage, and p\u2010tolylsulfonamide removal. A critical insight in the interrupted CuAAC reaction was proposed. Further prediction interprets H<jats:sub>2<\/jats:sub>O hydrogen bond chain plays an important role in C\u2212N bond formation and cleavage, and the removal of p\u2010tolylsulfonamide. This may have fundamental guidance on the design of 1, 5\u2010herterocyclic functionalized triazolopyrimidines via interrupted CuAAC rearrangement reaction, as well as hydrogen bond chain of water.<\/jats:p>","DOI":"10.1002\/cphc.202100751","type":"journal-article","created":{"date-parts":[[2021,11,20]],"date-time":"2021-11-20T04:10:47Z","timestamp":1637381447000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["A DFT Study on the Binuclear Copper(I)\u2010Catalyzed Synthesis Mechanism of 1,2,3\u2010Triazolo[1,5\u2010c]Pyrimidine via Interrupted Click and Ketenimine Rearrangement"],"prefix":"10.1002","volume":"23","author":[{"given":"Zhaoman","family":"Zhou","sequence":"first","affiliation":[{"name":"Department of Chemistry Key Laboratory of Surface &amp; Interface Science of Polymer Materials of Zhejiang Province Zhejiang Sci-Tech University  Hangzhou 310018 China"},{"name":"Office of Academic Research Guangxi Modern Polytechnic College  Hechi 547000 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qianqian","family":"Yue","sequence":"additional","affiliation":[{"name":"Department of Chemistry Key Laboratory of Surface &amp; Interface Science of Polymer Materials of Zhejiang Province Zhejiang Sci-Tech University  Hangzhou 310018 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2783-2443","authenticated-orcid":false,"given":"Yanying","family":"Zhao","sequence":"additional","affiliation":[{"name":"Department of Chemistry Key Laboratory of Surface &amp; Interface Science of Polymer Materials of Zhejiang Province Zhejiang Sci-Tech University  Hangzhou 310018 China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2021,12,16]]},"reference":[{"key":"e_1_2_9_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.196305651"},{"key":"e_1_2_9_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20010601)40:11<2004::AID-ANIE2004>3.0.CO;2-5"},{"key":"e_1_2_9_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20010601)113:11<2056::AID-ANGE2056>3.0.CO;2-W"},{"key":"e_1_2_9_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20020715)41:14<2596::AID-ANIE2596>3.0.CO;2-4"},{"key":"e_1_2_9_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20020715)114:14<2708::AID-ANGE2708>3.0.CO;2-0"},{"key":"e_1_2_9_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr800296p"},{"key":"e_1_2_9_5_1","first-page":"213","author":"Neto J. 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