Synthesis of Janus all-cis tetrafluorocyclohexanes carrying 1,4-diether motifs

Thomas Joseph Poskin; Bruno Piscelli; Aidan McKay; David Bradford Cordes; Yuto Eguchi; Shigeyuki Yamada; Rodrigo Cormanich; David O'Hagan

doi:10.1021/acs.joc.4c02345

Synthesis of Janus all-cis tetrafluorocyclohexanes carrying 1,4-diether motifs

Thomas Joseph Poskin
, Bruno Piscelli
, Aidan McKay
, David Bradford Cordes
, Yuto Eguchi
, Shigeyuki Yamada
, Rodrigo Cormanich
, David O'Hagan^*

^*Corresponding author for this work

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

Abstract

Nucleophilic aromatic substitutions (S_NAr) of alkoxides on pentafluoroaryl ethers are explored as a first step in a synthesis sequence to generate all-cis 2,3,5,6-tetrafluorocyclohexyl-1,4-dialkyl ethers 1. The S_NAr reaction was explored both experimentally and theoretically to rationalize ortho/para/meta selectivities. tert-Butyl deprotection of products followed by phenol alkylations introduces versatility to the synthesis. The final Rh(CAAC) 3 catalyzed aryl hydrogenation step of intermediate tetrafluoroaryl-1,4-diethers generated cyclohexane products 1. This chemistry introduces a new class of Janus fluorocyclohexane derivatives with ether substituents placed 1,4- to each other.

Original language	English
Number of pages	7
Journal	Journal of Organic Chemistry
Volume	ASAP
Early online date	27 Nov 2024
DOIs	https://doi.org/10.1021/acs.joc.4c02345
Publication status	E-pub ahead of print - 27 Nov 2024

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Poskin_2024_JoOC_Synthesis-Janus-all-cis-tetrafluorocyclohexanes-carrying-1,4-diether-motifs_CC
Copyright © 2024 The Authors. Published by American Chemical Society. This article is licensed under CC-BY 4.0 (https://creativecommons.org/licenses/by/4.0/).
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Janus faced fluorocyclohexanes: Properties and applications of Janus faced fluorocyclohexanes
O'Hagan, D. (PI)
1/12/19 → 14/03/23
Project: Standard

CCDC 2384410 & 2384411: Experimental Crystal Structure Determination
Poskin, T. J. (Creator), Piscelli, B. (Creator), Cordes, D. B. (Creator), Eguchi, Y. (Creator), Yamada, S. (Creator), Cormanich, R. (Creator), McKay, A. (Creator) & O'Hagan, D. (Creator), Cambridge Crystallographic Data Centre, 2024
DOI: 10.5517/ccdc.csd.cc2l15g9, https://dx.doi.org/10.5517/ccdc.csd.cc2l15hb
Dataset

Janus fluorocyclohexanes as facially polarised motifs for organized supramolecular materials
Poskin, T. J. (Author), O'Hagan, D. (Supervisor), 3 Jul 2025
Student thesis: Doctoral Thesis (PhD)

Cite this

@article{093fdf1900e6413ea9b1da35e75e6d90,

title = "Synthesis of Janus all-cis tetrafluorocyclohexanes carrying 1,4-diether motifs",

abstract = "Nucleophilic aromatic substitutions (SNAr) of alkoxides on pentafluoroaryl ethers are explored as a first step in a synthesis sequence to generate all-cis 2,3,5,6-tetrafluorocyclohexyl-1,4-dialkyl ethers 1. The SNAr reaction was explored both experimentally and theoretically to rationalize ortho/para/meta selectivities. tert-Butyl deprotection of products followed by phenol alkylations introduces versatility to the synthesis. The final Rh(CAAC) 3 catalyzed aryl hydrogenation step of intermediate tetrafluoroaryl-1,4-diethers generated cyclohexane products 1. This chemistry introduces a new class of Janus fluorocyclohexane derivatives with ether substituents placed 1,4- to each other.",

author = "Poskin, \{Thomas Joseph\} and Bruno Piscelli and Aidan McKay and Cordes, \{David Bradford\} and Yuto Eguchi and Shigeyuki Yamada and Rodrigo Cormanich and David O'Hagan",

note = "Funding: The authors thank EPSRC (EP/S030506) UK, and FAPESP Brazil are thanked for a Young Researcher Award to R.A.C. (\#2018/03910-1) and Scholarships to B.A.P. (\#2023/14064-2 and \#2022/10156-7). CNPq is acknowledged for a fellowship to R.A.C. (\#306912/2023-6) and FAEPEX for research funding. CENAPAD-SP and CESUP computational resources are also gratefully acknowledged.",

year = "2024",

month = nov,

day = "27",

doi = "10.1021/acs.joc.4c02345",

language = "English",

volume = "ASAP",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society (ACS)",

}

TY - JOUR

T1 - Synthesis of Janus all-cis tetrafluorocyclohexanes carrying 1,4-diether motifs

AU - Poskin, Thomas Joseph

AU - Piscelli, Bruno

AU - McKay, Aidan

AU - Cordes, David Bradford

AU - Eguchi, Yuto

AU - Yamada, Shigeyuki

AU - Cormanich, Rodrigo

AU - O'Hagan, David

N1 - Funding: The authors thank EPSRC (EP/S030506) UK, and FAPESP Brazil are thanked for a Young Researcher Award to R.A.C. (#2018/03910-1) and Scholarships to B.A.P. (#2023/14064-2 and #2022/10156-7). CNPq is acknowledged for a fellowship to R.A.C. (#306912/2023-6) and FAEPEX for research funding. CENAPAD-SP and CESUP computational resources are also gratefully acknowledged.

PY - 2024/11/27

Y1 - 2024/11/27

N2 - Nucleophilic aromatic substitutions (SNAr) of alkoxides on pentafluoroaryl ethers are explored as a first step in a synthesis sequence to generate all-cis 2,3,5,6-tetrafluorocyclohexyl-1,4-dialkyl ethers 1. The SNAr reaction was explored both experimentally and theoretically to rationalize ortho/para/meta selectivities. tert-Butyl deprotection of products followed by phenol alkylations introduces versatility to the synthesis. The final Rh(CAAC) 3 catalyzed aryl hydrogenation step of intermediate tetrafluoroaryl-1,4-diethers generated cyclohexane products 1. This chemistry introduces a new class of Janus fluorocyclohexane derivatives with ether substituents placed 1,4- to each other.

AB - Nucleophilic aromatic substitutions (SNAr) of alkoxides on pentafluoroaryl ethers are explored as a first step in a synthesis sequence to generate all-cis 2,3,5,6-tetrafluorocyclohexyl-1,4-dialkyl ethers 1. The SNAr reaction was explored both experimentally and theoretically to rationalize ortho/para/meta selectivities. tert-Butyl deprotection of products followed by phenol alkylations introduces versatility to the synthesis. The final Rh(CAAC) 3 catalyzed aryl hydrogenation step of intermediate tetrafluoroaryl-1,4-diethers generated cyclohexane products 1. This chemistry introduces a new class of Janus fluorocyclohexane derivatives with ether substituents placed 1,4- to each other.

U2 - 10.1021/acs.joc.4c02345

DO - 10.1021/acs.joc.4c02345

M3 - Article

SN - 0022-3263

VL - ASAP

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

ER -

Synthesis of Janus all-cis tetrafluorocyclohexanes carrying 1,4-diether motifs

Abstract

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Projects

Janus faced fluorocyclohexanes: Properties and applications of Janus faced fluorocyclohexanes

Datasets

CCDC 2384410 & 2384411: Experimental Crystal Structure Determination

Student theses

Janus fluorocyclohexanes as facially polarised motifs for organized supramolecular materials

Cite this