TY - JOUR
T1 - Organophotocatalytic dearomatization of indoles, pyrroles and benzo(thio)furans via a Giese-type transformation
AU - Zhang, Yueteng
AU - Ji, Peng
AU - Gao, Feng
AU - Dong, Yue
AU - Huang, He
AU - Wang, Changqing
AU - Zhou, Ziyuan
AU - Wang, Wei
N1 - Publisher Copyright:
© 2021, The Author(s).
PY - 2021/12
Y1 - 2021/12
N2 - Accessing fascinating organic and biological significant indolines via dearomatization of indoles represents one of the most efficient approaches. However, it has been difficult for the dearomatization of the electron deficient indoles. Here we report the studies leading to developing a photoredox mediated Giese-type transformation strategy for the dearomatization of the indoles. The reaction has been implemented for chemoselectively breaking indolyl C=C bonds embedded in the aromatic system. The synthetic power of this strategy has been demonstrated by using structurally diverse indoles bearing common electron-withdrawing groups including (thio)ester, amide, ketone, nitrile and even aromatics at either C2 or C3 positions and ubiquitous carboxylic acids as radical coupling partner with high trans-stereoselectivity (>20:1 dr). This manifold can also be applied to other aromatic heterocycles including pyrroles, benzofurans and benzothiophenes. Furthermore, enantioselective dearomatization of indoles has been achieved by a chiral camphorsultam auxiliary with high diastereoselectivity.
AB - Accessing fascinating organic and biological significant indolines via dearomatization of indoles represents one of the most efficient approaches. However, it has been difficult for the dearomatization of the electron deficient indoles. Here we report the studies leading to developing a photoredox mediated Giese-type transformation strategy for the dearomatization of the indoles. The reaction has been implemented for chemoselectively breaking indolyl C=C bonds embedded in the aromatic system. The synthetic power of this strategy has been demonstrated by using structurally diverse indoles bearing common electron-withdrawing groups including (thio)ester, amide, ketone, nitrile and even aromatics at either C2 or C3 positions and ubiquitous carboxylic acids as radical coupling partner with high trans-stereoselectivity (>20:1 dr). This manifold can also be applied to other aromatic heterocycles including pyrroles, benzofurans and benzothiophenes. Furthermore, enantioselective dearomatization of indoles has been achieved by a chiral camphorsultam auxiliary with high diastereoselectivity.
UR - http://www.scopus.com/inward/record.url?scp=85101280763&partnerID=8YFLogxK
U2 - 10.1038/s42004-021-00460-y
DO - 10.1038/s42004-021-00460-y
M3 - Article
AN - SCOPUS:85101280763
SN - 2399-3669
VL - 4
JO - Communications Chemistry
JF - Communications Chemistry
IS - 1
M1 - 20
ER -