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Synlett 2023; 34(18): 2210-2214
DOI: 10.1055/a-2071-4465
DOI: 10.1055/a-2071-4465
cluster
Modern Boron Chemistry: 60 Years of the Matteson Reaction
Direct α-Trifluoromethylthiolation of Carboxylic Acids Enabled by Boron Catalysis
This work was supported by the Japan Society for the Promotion of Science (JSPS KAKENHI Grant No. JP22H05329 in Digitalization-driven Transformative Organic Synthesis), Grant-in-Aid for Scientific Research (B) (No. JP20H02729), and Grant-in-Aid for Challenging Reserach (Exploratory, No. JP22K19016) to YS. CYH acknowledged the financial supports by Institute for Chemical Reaction Design and Discovery (WPI-ICReDD) and Hokkaido University.
Abstract
A boron-catalyzed direct α-trifluoromethylthiolation of carboxylic acids was developed. Catalytically generated boron enediolates reacts with electrophilic SCF3 reagent, N-SCF3-phthalimide, to provide α-SCF3 carboxylic acids without the need of substrate pre-activation. The method is applicable to direct modification of bioactive carboxylic acids. Data science analyses provided suitable models for substrate classification as well as yield prediction.
Key words
carboxylic acid - boron catalyst - trifluoromethylthiolation - data science - drug modification - fluorine compoundsSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2071-4465.
- Supporting Information
Publication History
Received: 13 March 2023
Accepted after revision: 11 April 2023
Accepted Manuscript online:
11 April 2023
Article published online:
15 May 2023
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- 14 General Procedure for α-Trifluoromethylthiolation of Carboxylic Acids Carboxylic acid (0.1 mmol, 1.0 equiv) was added to a 4 mL vial and then brought into the glove box. (AcO)4B2O (2.7 mg, 0.1 equiv), THF (1 mL), DBU (35.7 μL, 2.4 equiv), and N-(trifluoromethylthio)phthalimide (37.1 mg, 1.5 equiv) were sequentially added. The vial was sealed and removed from the glove box, and the resulting solution was stirred for 2 h at room temperature (23–28 ℃). MeI (37.4 μL, 6.0 equiv) was consequently added, and the reaction mixture was left stirred for another 2 h. Then, the reaction was worked up by adding 2 mL of 2:1:1 solution of brine, water, and 4 M HCl, followed by extraction with EtOAc (3 times). The combined organic layer was dried over Na2SO4, filtered, and concentrated in vacuo. To this crude product was added tetrabromoethane (11.6 μL, 0.1 mmol) and hexafluorobenzene (34.6 μL, 0.3 mmol) as the standards for the determination of NMR yield. The residue was then purified by silica gel chromatography on a Biotage Isolera One using a dry-load method.