CC BY-NC-ND 4.0 · Synlett 2023; 34(20): 2455-2460
DOI: 10.1055/a-2118-6813
cluster
Special Issue Dedicated to Prof. Hisashi Yamamoto

Synthesis of Halogen-Bond-Donor-Site-Introduced Functional Monomers through Wittig Reaction of Perfluorohalogenated Benzaldehydes: Toward Digitalization as Reliable Strategy in Small-Molecule Synthesis

Tatsuaki Hori
a   Institute for Molecular Science, Okazaki, Aichi 444-8787, Japan
b   SOKENDAI (The Graduate University for Advanced Studies), Okazaki, Aichi 444-8787, Japan
,
Shuya Kakinuma
a   Institute for Molecular Science, Okazaki, Aichi 444-8787, Japan
,
Naoya Ohtsuka
a   Institute for Molecular Science, Okazaki, Aichi 444-8787, Japan
b   SOKENDAI (The Graduate University for Advanced Studies), Okazaki, Aichi 444-8787, Japan
,
Takeshi Fujinami
a   Institute for Molecular Science, Okazaki, Aichi 444-8787, Japan
,
Toshiyasu Suzuki
a   Institute for Molecular Science, Okazaki, Aichi 444-8787, Japan
,
a   Institute for Molecular Science, Okazaki, Aichi 444-8787, Japan
b   SOKENDAI (The Graduate University for Advanced Studies), Okazaki, Aichi 444-8787, Japan
› Author Affiliations
This work was partially supported by the ASAHI GLASS Foundation, the NAGAI Foundation for Science and Technology, a Grant-in-Aid for Precise Formation of a Catalyst Having a Specified Field for Use in Extremely Difficult Substrate Conversion Reactions (KAKENHI Grant No. 18H04275), and the Grant-in-Aid for Transformative Organic Synthesis (Digi-TOS) (KAKENHI Grant No. 21H05218) from the Ministry of Education, Culture, Sports, Science and Technology, Japan. N.M. and T.F. gratefully acknowledge JST-ACCEL for their financial support.


This paper is dedicated to Professor Hisashi Yamamoto in celebration of his 80th birthday.

Abstract

The Wittig reaction of perfluoromonohalobenzaldehydes was systematically studied to synthesize 2,3,5,6-tetrafluoro-4-halostyrene (TFXSs) as functional monomers bearing halogen-bond donor sites. The reaction proceeded efficiently in tetrahydrofuran using 1,1,3,3-tetramethylguanidine as an organic base. Correlation analysis quantitatively identified three key factors required to obtain TFXSs in reasonable yields. The present approach not only contributes to the study of halogen-bond-based functional molecules, but also presents digitalization as a potential strategy in small-molecule synthesis.

Supporting Information



Publication History

Received: 17 May 2023

Accepted after revision: 26 June 2023

Accepted Manuscript online:
27 June 2023

Article published online:
17 August 2023

© 2023. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution-NonDerivative-NonCommercial-License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by-nc-nd/4.0/)

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