“Cyclopropanation of Cyclopropanes”: GaCl3‑Mediated Ionic Cyclopropanation of Donor–Acceptor Cyclopropanes with Diazo Esters as a Route to Tetrasubstituted Activated Cyclopropanes

• Published in: Journal of organic chemistry Vol. 86; no. 6; pp. 4567 - 4579
• Main Authors: Borisova, Irina A, Ratova, Daria-Maria V, Potapov, Konstantin V, Tarasova, Anna V, Novikov, Roman A, Tomilov, Yury V
• Format: Journal Article
• Language: English
• Published: American Chemical Society 19-03-2021
• Subjects: Diazo esters; Gallium trichloride; Titanium tetrachloride; Ionic cyclopropanation; 1,2-Zwitterionic intermediates; Tetrasubstituted cyclopropanes; Donor–acceptor cyclopropanes; Lactones
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.0c02983

A new ionic cyclopropanation process involving the addition of diazo esters to donor–acceptor cyclopropanes (DAC) activated by GaCl3 has been developed. The reactions occur via 1,2-zwitterionic gallium complexes with elimination of nitrogen in all cases to give 1,1,2,3-tetrasubstituted cyclopropanes as the main products. Also, a number of related processes with the formation of various polysubstituted cyclopropanes, alkenes, and cyclobutanes, including products of multiple diazo ester addition, have been developed. Obtained by the developed method tetrasubstituted cyclopropanes are activated cyclopropanes such as DAC and can be used for further synthesis in this capacity. Their new reaction with benzaldehyde promoted by TiCl4 and involving one of the additional functional groups has been demonstrated, which leads to five-membered lactones. The mechanisms of the occurring processes, as well as the structures and stereochemistry of a rich range of products formed, are discussed in detail.