Probing the Peroxycarbenium [3+2] Cycloaddition Reactions with 1,2‐Disubstituted Ethylenes: Results and Insights

• Published in: Chemistry : a European journal Vol. 23; no. 9; pp. 2031 - 2034
• Main Authors: Xu, Ze‐Jun, Wittlin, Sergio, Wu, Yikang
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 10.02.2017; Wiley Subscription Services, Inc
• Subjects: Alkenes; Bonding; Carbon; Chemical bonds; Chemistry; Chemistry, Multidisciplinary; Cycloaddition; Oxygen; Oxygen atoms; peroxides; Physical Sciences; rearrangement; ring expansion; Science & Technology; Terminals; ORGANIC PEROXIDES; cycloaddition; SINGLE; ring expansion; C BOND FORMATION; MALARIA; ANTIMALARIAL PEROXIDES; alkenes; peroxides; 1,2-DIOXOLANES; rearrangement
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201605871

The causes for the title reaction to be limited to only the alkenes with an unsubstituted terminal alkenic carbon were explored. In some “failed” cases the cycloaddition products actually formed but rearranged concurrently. An oxygen atom or a N‐Boc (Boc=tert‐butyloxycarbonyl) group at the double bond was proven essential for acquisition of intact [3+2] cycloaddition products from 1,2‐disubstituted ethylenes. Mission impossible: The peroxycarbenium [3+2] cycloaddition reaction with 1,2‐disubstituted ethylenes, an impossible challenge to date, was achieved for the first time. An oxygen or N‐Boc group at the double bond was proven essential for the acquisition of intact cycloaddition products. Otherwise, the cycloaddition may “fail” because product rearranged completely even at low temperatures.