Premium
A Simple, Serendipitous Synthesis of Heterohexahelicenes
Author(s) -
Dougherty Kelly J.,
Qin Qian,
Cruz Ricardo,
Cho Yeyoung,
Donahue James P.,
Mague Joel T.,
Wilson Laura J.,
Kraml Christina M.,
Pascal Robert A.
Publication year - 2019
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201901207
Subject(s) - halogenation , chemistry , thiophene , stereochemistry , extrusion , combinatorial chemistry , organic chemistry , medicinal chemistry , computational chemistry , metallurgy , materials science
Oxidation of benzo[1,2‐ b :3,4‐ b ′:5,6‐ b ′′]trithiophene ( 1 ) with MCPBA at room temperature gives the corresponding monosulfone 3 . This material readily undergoes a Diels–Alder dimerization with extrusion of SO 2 to form the dihydroheterohelicene 5 . This, in turn, is easily converted into the heterohelicene 6 in a one‐pot NBS bromination and elimination. In a similar manner, oxidation of phenanthro[9,10‐ b ]thiophene ( 12 ) gives the dihydroheterohelicene 13 , and bromination/elimination forms the corresponding heterohelicene 8 . The X‐ray structures of compounds 5 , 6 , and 13 are reported, as well as computational studies that illuminate the unusual regiochemical outcome of the dimerization reactions.