文献类型：期刊文献

英文题名：In(OTf)3-Catalyzed (3+3) Dipolar Cyclization of Bicyclo[1.1.0]butanes with N-Nucleophilic 1,3-Dipoles: Access to 2,3-Diazabicyclo[3.1.1]heptanes, 2,3-Diazabicyclo[3.1.1]heptenes, and Enantiopure 2-Azabicyclo[3.1.1]heptanes

作者：Zhang, Jian[1];Su, Jia-Yi[2];Zheng, Hanliang[1];Li, Hao[2];Deng, Wei-Ping[1]

机构：[1]Zhejiang Normal Univ, Coll Chem & Mat Sci, Key Lab Minist Educ Adv Catalysis Mat, Jinhua 321004, Peoples R China;[2]East China Univ Sci & Technol, Sch Pharm, Shanghai Key Lab New Drug Design, Shanghai 200237, Peoples R China

年份：2024

卷号：14

期号：23

起止页码：17837

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20244817418673);WOS:【SCI-EXPANDED(收录号:WOS:001358965100001)】；

基金：We are grateful to the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang (No. 2022R01007), the National Key Research and Development Program of China (2021YFA0804900), and the Start-up Research Grant from Zhejiang Normal University for financial support.

语种：英文

外文关键词：bridged bicyclic scaffolds; strained molecules; dipolar cyclization; bicyclo[1.1.0]butanes; asymmetriccatalysis

摘要：The investigation into the synthesis of azabicyclo[3.1.1]heptanes (azaBCHeps) as bioisosteres to flat aza-aromatics has garnered increasing attention, while it encounters significant challenges. Herein, we have demonstrated the In(OTf)3-catalyzed (3 + 3) dipolar cyclization of bicyclo[1.1.0]butanes (BCBs) with hydrazones and pi-allyl-iridium 1,3-dipoles, engendering a diverse array of azaBCHeps. The cyclization of hydrazones and BCBs furnished densely substituted 2,3-diazabicyclo[3.1.1]heptanes and 2,3-diazabicyclo[3.1.1]heptenes under nitrogen and oxygen atmospheres, respectively. A combination of experimental and computational investigations lends robust support for the proton-transfer-interposed sequential mechanism. More importantly, by integrating In(OTf)3/iridium relay catalysis, enantiopure 2-azabicyclo[3.1.1]heptanes were constructed through the (3 + 3) cyclization of BCBs with aza-pi-allyl-iridium 1,3-dipoles, in situ generated from N-allyl carbonates. Both methodologies exhibit mild reaction conditions and good tolerance for various functional groups. Moreover, the copious derivatization of products highlights the utility of the newly synthesized heterobicyclic motifs as versatile building blocks in synthetic chemistry.