2,2′-Biphenol-Derived Phosphoric Acid Catalyst for the Dehydrative Esterification of Carboxylic Acids with Alcohols

Manabu Hatano; Chiaki Nishioka; Ayaka Mimura; Risa Kimura; Yuki Okuda; Takeshi Yamada; Ken Sakata

doi:10.1055/s-0042-1752738

Synlett, Table of Contents

Synlett 2023; 34(20): 2508-2514
DOI: 10.1055/s-0042-1752738

cluster

Special Issue Dedicated to Prof. Hisashi Yamamoto

2,2′-Biphenol-Derived Phosphoric Acid Catalyst for the Dehydrative Esterification of Carboxylic Acids with Alcohols

Manabu Hatano ∗

^aFaculty of Pharmaceutical Sciences, Kobe Pharmaceutical University, 4-19-1, Motoyamakita-machi, Higashinada, Kobe 658-8558, Japan

,

Chiaki Nishioka

^aFaculty of Pharmaceutical Sciences, Kobe Pharmaceutical University, 4-19-1, Motoyamakita-machi, Higashinada, Kobe 658-8558, Japan

,

Ayaka Mimura

^aFaculty of Pharmaceutical Sciences, Kobe Pharmaceutical University, 4-19-1, Motoyamakita-machi, Higashinada, Kobe 658-8558, Japan

,

Risa Kimura

^aFaculty of Pharmaceutical Sciences, Kobe Pharmaceutical University, 4-19-1, Motoyamakita-machi, Higashinada, Kobe 658-8558, Japan

,

Yuki Okuda

^aFaculty of Pharmaceutical Sciences, Kobe Pharmaceutical University, 4-19-1, Motoyamakita-machi, Higashinada, Kobe 658-8558, Japan

,

Takeshi Yamada

^aFaculty of Pharmaceutical Sciences, Kobe Pharmaceutical University, 4-19-1, Motoyamakita-machi, Higashinada, Kobe 658-8558, Japan

,

Ken Sakata ∗

^bFaculty of Pharmaceutical Sciences, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan

› Author Affiliations

Abstract

All articles of this category

Dedicated to Professor Hisashi Yamamoto on the occasion of his 80^th birthday

Abstract

A dehydrative esterification from an equimolar mixture of carboxylic acids and primary or secondary alcohols in toluene at 100 °C was promoted without the necessity to remove water by using a simple 2,2′-biphenol-derived phosphoric acid catalyst (2.5–10 mol%). This reaction was also successfully conducted at the gram scale. To demonstrate the synthetic utility of this catalytic system, pharmaceutically useful substrates and acid-sensitive substrates were examined using these acid–base cooperative phosphoric acid catalysts, which exhibit relatively weak Brønsted acidity.

Key words

alcohols - carboxylic acids - DFT calculations - esterification - green chemistry - organocatalysts - phosphoric acid - pK _a

Full Text

References

References and Notes

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14 Compound 1e and its conjugate base can adopt various stable structures with relatively small energy differences. We estimated the pK _a value by using both the structure of 1e with the lowest free energy (I) and the structure of the conjugated base with the lowest energy (XI); for details, see the Supporting Information.
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16 The difference in the dihedral angle of the biaryl moiety in catalysts 1h (43.5°) and 1i (53.2°) can be expected to partially affect the structural rigidity of 1h and 1i. The dihedral angle of the biaryl moiety in 1j is 53.1°. Therefore, the stronger Brønsted acidity (i.e., pK _a) of 1j compared to that of 1i might be reflected in the catalytic activity; for details, see the Supporting Information.
17 EtOAc does not react with alcohols under our catalytic conditions, and the source of the acetyl moiety of AcOBn (4aa) is AcOH (2a) in Scheme 1. Actually, in Scheme 4, when the reaction of 2l and 3a in EtOAc was performed, 4la was obtained in 90% yield and 4aa was not obtained.

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23 Since catalysts 1e and 1h were soluble under our reaction conditions at 80–100 °C, the yields of the products in Scheme 6 might not simply depend on the solubility of the catalysts. At the present preliminary stage, we cannot clearly explain the observed results in Scheme 6, and pK _a value, the basicity of the P=O moiety, homodimerization, and conformational flexibility of the catalysts and the instability of the starting materials and products might complicate the results.
24 General Procedure: A thoroughly flame-dried, two-necked flask with a condenser was charged with catalyst 1h (12.4 mg, 0.050 mmol, 5 mol%) under an argon atmosphere. Toluene (2 mL), carboxylic acid 2 (1.0 mmol), and alcohol 3 (1.0 mmol) were added at room temperature. The mixture was then stirred at 100 °C (bath temperature) for the indicated reaction time (6–72 h), and the reaction was monitored by TLC. Subsequently, the mixture was cooled to room temperature and concentrated under reduced pressure. The crude product was purified by column chromatography on silica gel (n-hexane/EtOAc, 20:1 to 5:1) to give 4. For characterization data and copies of NMR spectra, see the Supporting Information.

Supplementary Material

Supporting Information