TY - JOUR
T1 - A new chiral phenomenon of orientational chirality, its synthetic control and computational study
AU - Jin, Shengzhou
AU - Xu, Ting
AU - Tang, Yao
AU - Wang, Jia Yin
AU - Wang, Yu
AU - Pan, Junyi
AU - Zhang, Sai
AU - Yuan, Qingkai
AU - Rahman, Anis Ur
AU - Aquino, Adelia J.A.
AU - Lischka, Hans
AU - Li, Guigen
N1 - Publisher Copyright:
Copyright © 2023 Jin, Xu, Tang, Wang, Wang, Pan, Zhang, Yuan, Rahman, Aquino, Lischka and Li.
PY - 2023/1/5
Y1 - 2023/1/5
N2 - A new type of chirality, orientational chirality, consisting of a tetrahedron center and a remotely anchored blocker, has been discovered. The key structural element of this chirality is characterized by multiple orientations directed by a through-space functional group. The multi-step synthesis of orientational chiral targets was conducted by taking advantage of asymmetric nucleophilic addition, Suzuki-Miyaura cross-coupling and Sonogashira coupling. An unprecedented catalytic species showing a five-membered ring consisting of C (sp2)-Br-Pd-C (sp2) bonds was isolated during performing Suzuki-Miyaura cross-coupling. X-ray diffraction analysis confirmed the species structure and absolute configuration of chiral orientation products. Based on X-ray structures, a model was proposed for the new chirality phenomenon to differentiate the present molecular framework from previous others. DFT computational study presented the relative stability of individual orientatiomers. This discovery would be anticipated to result in a new stereochemistry branch and to have a broad impact on chemical, biomedical, and material sciences in the future.
AB - A new type of chirality, orientational chirality, consisting of a tetrahedron center and a remotely anchored blocker, has been discovered. The key structural element of this chirality is characterized by multiple orientations directed by a through-space functional group. The multi-step synthesis of orientational chiral targets was conducted by taking advantage of asymmetric nucleophilic addition, Suzuki-Miyaura cross-coupling and Sonogashira coupling. An unprecedented catalytic species showing a five-membered ring consisting of C (sp2)-Br-Pd-C (sp2) bonds was isolated during performing Suzuki-Miyaura cross-coupling. X-ray diffraction analysis confirmed the species structure and absolute configuration of chiral orientation products. Based on X-ray structures, a model was proposed for the new chirality phenomenon to differentiate the present molecular framework from previous others. DFT computational study presented the relative stability of individual orientatiomers. This discovery would be anticipated to result in a new stereochemistry branch and to have a broad impact on chemical, biomedical, and material sciences in the future.
KW - and sonogashira coupling
KW - atropisomerism
KW - orientational chirality
KW - rotamer
KW - suzuki-miyaura coupling
UR - http://www.scopus.com/inward/record.url?scp=85146512784&partnerID=8YFLogxK
U2 - 10.3389/fchem.2022.1110240
DO - 10.3389/fchem.2022.1110240
M3 - Article
AN - SCOPUS:85146512784
SN - 2296-2646
VL - 10
JO - Frontiers in Chemistry
JF - Frontiers in Chemistry
M1 - 1110240
ER -