[RhIII(Cp*)]-catalyzed arylfluorination of α-diazoketoesters for facile synthesis of α-aryl-α-fluoroketoesters

Fo-Ning Ng; Chun-Ming Chan; Jianbin Li; Mingzi Sun; Yin-Suo Lu; Zhongyuan Zhou; Bolong Huang; Wing-Yiu Yu

doi:10.1039/c8ob02801j

[Rh^III(Cp*)]-catalyzed arylfluorination of α-diazoketoesters for facile synthesis of α-aryl-α-fluoroketoesters

Fo-Ning Ng
, Chun-Ming Chan
, Jianbin Li
, Mingzi Sun
, Yin-Suo Lu
, Zhongyuan Zhou
, Bolong Huang^*
, Wing-Yiu Yu

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

11 Citations (Scopus)

Abstract

Here we describe the Cp∗Rh(iii)-catalyzed cascade arylfluorination reactions of α-diazoketoesters with arylboronic acids and N-fluorobenzenesulfonimide for one-pot C(sp ³ )-C(aryl) and C(sp ³ )-F bond formation. The arylfluorination reaction can be accomplished with remarkable chemo- and regioselectivity. Our mechanistic investigation showed that the Rh-catalyzed arylfluorination of diazoacetates occurred by (1) transmetalation of arylboronic acids to form an arylrhodium(iii) complex, (2) coupling of diazomalonates with the arylrhodium(iii) complex to form carbene-rhodium, (3) migratory carbene insertion to form a diketonato-rhodium(iii) complex-probably via rearrangement of the putative σ-alkylrhodium(iii) complex, and (4) electrophilic fluorination of the diketonato-rhodium to form the α-aryl-α-fluoromalonates. ©2019 The Royal Society of Chemistry.

Original language	English
Pages (from-to)	1192-1201
Journal	Organic and Biomolecular Chemistry
Volume	17
Issue number	5
DOIs	https://doi.org/10.1039/c8ob02801j
Publication status	Published - 2019
Externally published	Yes

Bibliographical note

Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to [email protected].

Funding

We thank The Hong Kong Research Grants Council (PolyU5032/13P; 153152/16P 153023/17P and C5023-14G) for financial support.

RGC Funding Information

RGC-funded

Access Output

10.1039/c8ob02801j

Other Access Options

Check CityUHK Library

Permanent Link

Right click to copy link

Cite this

@article{1bacb64e606440eb9ae5f03bb2eaba44,

title = "[RhIII(Cp*)]-catalyzed arylfluorination of α-diazoketoesters for facile synthesis of α-aryl-α-fluoroketoesters",

abstract = "Here we describe the Cp∗Rh(iii)-catalyzed cascade arylfluorination reactions of α-diazoketoesters with arylboronic acids and N-fluorobenzenesulfonimide for one-pot C(sp 3 )-C(aryl) and C(sp 3 )-F bond formation. The arylfluorination reaction can be accomplished with remarkable chemo- and regioselectivity. Our mechanistic investigation showed that the Rh-catalyzed arylfluorination of diazoacetates occurred by (1) transmetalation of arylboronic acids to form an arylrhodium(iii) complex, (2) coupling of diazomalonates with the arylrhodium(iii) complex to form carbene-rhodium, (3) migratory carbene insertion to form a diketonato-rhodium(iii) complex-probably via rearrangement of the putative σ-alkylrhodium(iii) complex, and (4) electrophilic fluorination of the diketonato-rhodium to form the α-aryl-α-fluoromalonates. {\textcopyright}2019 The Royal Society of Chemistry.",

author = "Fo-Ning Ng and Chun-Ming Chan and Jianbin Li and Mingzi Sun and Yin-Suo Lu and Zhongyuan Zhou and Bolong Huang and Wing-Yiu Yu",

note = "Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to [email protected].",

year = "2019",

doi = "10.1039/c8ob02801j",

language = "English",

volume = "17",

pages = "1192--1201",

journal = "Organic and Biomolecular Chemistry",

issn = "1477-0520",

publisher = "Royal Society of Chemistry",

number = "5",

}

TY - JOUR

T1 - [RhIII(Cp*)]-catalyzed arylfluorination of α-diazoketoesters for facile synthesis of α-aryl-α-fluoroketoesters

AU - Ng, Fo-Ning

AU - Chan, Chun-Ming

AU - Li, Jianbin

AU - Sun, Mingzi

AU - Lu, Yin-Suo

AU - Zhou, Zhongyuan

AU - Huang, Bolong

AU - Yu, Wing-Yiu

N1 - Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to [email protected].

PY - 2019

Y1 - 2019

N2 - Here we describe the Cp∗Rh(iii)-catalyzed cascade arylfluorination reactions of α-diazoketoesters with arylboronic acids and N-fluorobenzenesulfonimide for one-pot C(sp 3 )-C(aryl) and C(sp 3 )-F bond formation. The arylfluorination reaction can be accomplished with remarkable chemo- and regioselectivity. Our mechanistic investigation showed that the Rh-catalyzed arylfluorination of diazoacetates occurred by (1) transmetalation of arylboronic acids to form an arylrhodium(iii) complex, (2) coupling of diazomalonates with the arylrhodium(iii) complex to form carbene-rhodium, (3) migratory carbene insertion to form a diketonato-rhodium(iii) complex-probably via rearrangement of the putative σ-alkylrhodium(iii) complex, and (4) electrophilic fluorination of the diketonato-rhodium to form the α-aryl-α-fluoromalonates. ©2019 The Royal Society of Chemistry.

AB - Here we describe the Cp∗Rh(iii)-catalyzed cascade arylfluorination reactions of α-diazoketoesters with arylboronic acids and N-fluorobenzenesulfonimide for one-pot C(sp 3 )-C(aryl) and C(sp 3 )-F bond formation. The arylfluorination reaction can be accomplished with remarkable chemo- and regioselectivity. Our mechanistic investigation showed that the Rh-catalyzed arylfluorination of diazoacetates occurred by (1) transmetalation of arylboronic acids to form an arylrhodium(iii) complex, (2) coupling of diazomalonates with the arylrhodium(iii) complex to form carbene-rhodium, (3) migratory carbene insertion to form a diketonato-rhodium(iii) complex-probably via rearrangement of the putative σ-alkylrhodium(iii) complex, and (4) electrophilic fluorination of the diketonato-rhodium to form the α-aryl-α-fluoromalonates. ©2019 The Royal Society of Chemistry.

UR - https://www.scopus.com/pages/publications/85060952785

UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-85060952785&origin=recordpage

U2 - 10.1039/c8ob02801j

DO - 10.1039/c8ob02801j

M3 - RGC 21 - Publication in refereed journal

C2 - 30648165

SN - 1477-0520

VL - 17

SP - 1192

EP - 1201

JO - Organic and Biomolecular Chemistry

JF - Organic and Biomolecular Chemistry

IS - 5

ER -