Effects of water addition on a catalytic fluorination of dienamine

Daiki Kuraoku; Tsunaki Yonamine; Genta Koja; Norio Yoshida; Satoru Arimitsu; Masahiro Higashi

doi:10.3390/molecules24193428

Effects of water addition on a catalytic fluorination of dienamine

Daiki Kuraoku, Tsunaki Yonamine, Genta Koja, Norio Yoshida, Satoru Arimitsu, Masahiro Higashi

Multidisciplinary chemistry

Research output: Contribution to journal › Article › peer-review

4 Citations (Scopus)

Abstract

We investigate the effects of water addition on a highly stereocontrolled fluorination of dienamine generated by α-branched enals and 60-hydroxy-9-amino-9-deoxy-epi-quinidine with N-fluorobenzenesulfonimide (NFSI) in the presence of Brønsted acid both experimentally and theoretically. It is experimentally found that water addition to organic solvent significantly shortens the reaction time whereas excessive water addition decreases the enantiomeric excess. The results calculated with three-dimensional reference interaction site model self-consistent field (3D-RISM-SCF) method are in good agreement with the experimental ones. It is revealed that the shortness of reaction time is caused by the reactant destabilization and that the decrease in enantiomeric excess is due to the difference of hydration free energy between two transition states.

Original language	English
Article number	3428
Journal	Molecules
Volume	24
Issue number	19
DOIs	https://doi.org/10.3390/molecules24193428
Publication status	Published - Sept 21 2019

All Science Journal Classification (ASJC) codes

Analytical Chemistry
Chemistry (miscellaneous)
Molecular Medicine
Pharmaceutical Science
Drug Discovery
Physical and Theoretical Chemistry
Organic Chemistry

Access to Document

10.3390/molecules24193428

Cite this

@article{af8c3d3a6fea4d99a5b51c0149d142ba,

title = "Effects of water addition on a catalytic fluorination of dienamine",

abstract = "We investigate the effects of water addition on a highly stereocontrolled fluorination of dienamine generated by α-branched enals and 60-hydroxy-9-amino-9-deoxy-epi-quinidine with N-fluorobenzenesulfonimide (NFSI) in the presence of Br{\o}nsted acid both experimentally and theoretically. It is experimentally found that water addition to organic solvent significantly shortens the reaction time whereas excessive water addition decreases the enantiomeric excess. The results calculated with three-dimensional reference interaction site model self-consistent field (3D-RISM-SCF) method are in good agreement with the experimental ones. It is revealed that the shortness of reaction time is caused by the reactant destabilization and that the decrease in enantiomeric excess is due to the difference of hydration free energy between two transition states.",

author = "Daiki Kuraoku and Tsunaki Yonamine and Genta Koja and Norio Yoshida and Satoru Arimitsu and Masahiro Higashi",

note = "Funding Information: Funding: This research was supported by JSPS KAKENHI Grant Numbers 16KT0165, 17K05757, as well as JSPS KAKENHI Grant 18H04657 in the Innovative Area “Hybrid Catalysis”. Publisher Copyright: {\textcopyright} 2019 by the authors.",

year = "2019",

month = sep,

day = "21",

doi = "10.3390/molecules24193428",

language = "English",

volume = "24",

journal = "Molecules",

issn = "1420-3049",

publisher = "Multidisciplinary Digital Publishing Institute (MDPI)",

number = "19",

}

TY - JOUR

T1 - Effects of water addition on a catalytic fluorination of dienamine

AU - Kuraoku, Daiki

AU - Yonamine, Tsunaki

AU - Koja, Genta

AU - Yoshida, Norio

AU - Arimitsu, Satoru

AU - Higashi, Masahiro

N1 - Funding Information: Funding: This research was supported by JSPS KAKENHI Grant Numbers 16KT0165, 17K05757, as well as JSPS KAKENHI Grant 18H04657 in the Innovative Area “Hybrid Catalysis”. Publisher Copyright: © 2019 by the authors.

PY - 2019/9/21

Y1 - 2019/9/21

N2 - We investigate the effects of water addition on a highly stereocontrolled fluorination of dienamine generated by α-branched enals and 60-hydroxy-9-amino-9-deoxy-epi-quinidine with N-fluorobenzenesulfonimide (NFSI) in the presence of Brønsted acid both experimentally and theoretically. It is experimentally found that water addition to organic solvent significantly shortens the reaction time whereas excessive water addition decreases the enantiomeric excess. The results calculated with three-dimensional reference interaction site model self-consistent field (3D-RISM-SCF) method are in good agreement with the experimental ones. It is revealed that the shortness of reaction time is caused by the reactant destabilization and that the decrease in enantiomeric excess is due to the difference of hydration free energy between two transition states.

AB - We investigate the effects of water addition on a highly stereocontrolled fluorination of dienamine generated by α-branched enals and 60-hydroxy-9-amino-9-deoxy-epi-quinidine with N-fluorobenzenesulfonimide (NFSI) in the presence of Brønsted acid both experimentally and theoretically. It is experimentally found that water addition to organic solvent significantly shortens the reaction time whereas excessive water addition decreases the enantiomeric excess. The results calculated with three-dimensional reference interaction site model self-consistent field (3D-RISM-SCF) method are in good agreement with the experimental ones. It is revealed that the shortness of reaction time is caused by the reactant destabilization and that the decrease in enantiomeric excess is due to the difference of hydration free energy between two transition states.

UR - http://www.scopus.com/inward/record.url?scp=85072575580&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85072575580&partnerID=8YFLogxK

U2 - 10.3390/molecules24193428

DO - 10.3390/molecules24193428

M3 - Article

C2 - 31546593

AN - SCOPUS:85072575580

SN - 1420-3049

VL - 24

JO - Molecules

JF - Molecules

IS - 19

M1 - 3428

ER -

Effects of water addition on a catalytic fluorination of dienamine

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this