School of Chemistry, Analytical and Biological Chemistry Research Facility, University College Cork, Cork, Ireland.
School of Chemistry, Analytical and Biological Chemistry Research Facility, Synthesis and Solid State Pharmaceutical Centre, University College Cork, Cork, Ireland.
J Org Chem. 2021 Oct 15;86(20):13955-13982. doi: 10.1021/acs.joc.1c01310. Epub 2021 Aug 11.
Generation and use of triflyl azide in flow enables efficient synthesis of a range of α-diazocarbonyl compounds, including α-diazoketones, α-diazoamides, and an α-diazosulfonyl ester, via both Regitz-type diazo transfer and deacylative/debenzoylative diazo-transfer processes with excellent yields and offers versatility in the solvent employed, in addition to addressing the hazards associated with handling of this highly reactive sulfonyl azide. Telescoping the generation of triflyl azide and diazo-transfer process with highly enantioselective copper-mediated intramolecular aromatic addition and C-H insertion processes demonstrates that the reaction stream containing the α-diazocarbonyl compound can be obtained in sufficient purity to pass directly over the immobilized copper bis(oxazoline) catalyst without detrimentally impacting the catalyst enantioselectivity.
在流动相中生成和使用三氟甲磺酸叠氮化物，可通过 Regitz 型重氮转移和去酰基/去苯甲酰基重氮转移过程，高效合成一系列α-二羰基化合物，包括α-二氮酮、α-二氮酰胺和α-二氮磺酰酯，具有优异的收率，并在溶剂的使用方面具有多功能性，此外还解决了处理这种高反应性的磺酰叠氮化物所带来的危害。将三氟甲磺酸叠氮化物的生成与高对映选择性铜介导的分子内芳香加成和 C-H 插入过程相缩合，表明含有α-二羰基化合物的反应流可以获得足够的纯度，直接通过固定化铜双（恶唑啉）催化剂而不会对催化剂对映选择性产生不利影响。
