Tu Hang-Fei, Jeandin Aliénor, Suero Marcos G
Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Països Catalans 16, 43007 Tarragona, Spain.
Departament de Química Analítica i Química Orgánica, Universitat Rovira i Virgili, Calle Marcel.lí Domingo, 1, 43007 Tarragona, Spain.
J Am Chem Soc. 2022 Sep 21;144(37):16737-16743. doi: 10.1021/jacs.2c07769. Epub 2022 Sep 8.
Herein, we report the first catalytic one-step synthesis of cyclopropenium cations (CPCs) with readily available alkynes and hypervalent iodine reagents as carbyne sources. Key to the process is the catalytic generation of a novel Rh-carbynoid that formally transfers monovalent cationic carbynes (:C-R) to alkynes via an oxidative [2+1] cycloaddition. Our process is able to synthesize a new type of CPC substituted with an ester group that underpins the regioselective attack of a broad range of carbon and heteroatomic nucleophiles, thus providing a new platform for the synthesis of valuable cyclopropenes difficult or not possible to make by current methodologies.
在此，我们报道了首例以易于获得的炔烃和高价碘试剂作为卡宾源，通过催化一步法合成环丙烯鎓阳离子（CPCs）。该过程的关键在于催化生成一种新型铑卡宾体，其通过氧化[2 + 1]环加成将单价阳离子卡宾（:C-R）正式转移至炔烃。我们的方法能够合成一种新型的带有酯基取代的CPC，这为广泛的碳和杂原子亲核试剂的区域选择性进攻奠定了基础，从而为合成目前方法难以制备或无法制备的有价值的环丙烯提供了一个新平台。
