The Synthesis and Properties of Methylenecyclopropane¹

Olefin Cyclopropanation by a Sequential Atom‐Transfer Radical Addition and Dechlorination in the Presence of a Ruthenium Catalyst

“…Cyclopropanes can also be synthesized by reductive coupling of 1,3‐dihalogen derivatives. Reagents, which can induce this transformation, include metals such as Na,2 Mg,3 or Zn,4 alkyllithium,5 and Grignard compounds,6 and transition metal complexes,7 among others 8. However, dehalogenation reactions are not very popular for synthetic applications.…”

Heterocycles from methylenecyclopropanes

“…Their stability began to be realized by people after the discovery of many natural products containing MCP skeletons, such as hypoglycine and methylenecyclopropylglycine. 1 The parent structure of MCPs were successfully synthesized in laboratory for the first time in 1953 by treating 3-chloro-(2chloromethyl)-1-propene with Mg. 2 During the following several decades, a series of comprehensive methodologies for MCP synthesis have been developed, 3 making these highly strained molecules readily accessible materials in laboratory. Nowadays, MCPs have been widely applied in organic synthesis, 4 pharmaceutical chemistry, 5 agricultural chemistry 6 and even material science.…”

Olefin Cyclopropanations via Sequential Atom Transfer Radical Addition-Dechlorination Reactions

“…The addition products are 1,3-dihalides. It had been reported that in the presence of various metals, such as Na, [9] Mg, [10] Zn, [11] Grignard compounds, [12] or transition metal complexes, [13] cyclopropanes can be obtained by reductive coupling of 1,3-dihalogen derivatives. We were thus interested to explore the possibility to combine Ru-catalyzed ATRA and ATRC reactions with a dehalogenation step to produce cyclopropanes.…”