Alcohol-Directed ortho-C–H Alkenylation

Li Li; Qinglan Liu; Jiean Chen; Yong Huang

doi:10.1055/s-0037-1611538

Synlett, Table of Contents

Synlett 2019; 30(11): 1366-1370
DOI: 10.1055/s-0037-1611538

letter

Alcohol-Directed ortho-C–H Alkenylation

Li Li

,

Qinglan Liu

,

Jiean Chen *

State Key Laboratory of Chemical Oncogenomics, Key Laboratory of Chemical Genomics, Peking University, Shenzhen Graduate School, Shenzhen 518055, P. R. of China Email: chenja@pkusz.edu.cn Email: huangyong@pkusz.edu.cn

,

Yong Huang *

State Key Laboratory of Chemical Oncogenomics, Key Laboratory of Chemical Genomics, Peking University, Shenzhen Graduate School, Shenzhen 518055, P. R. of China Email: chenja@pkusz.edu.cn Email: huangyong@pkusz.edu.cn

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Abstract

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Abstract

We report a simple and mild dehydrogenative cross-coupling reaction of unprotected arylethanols and acrylates. Unlike the case of previous reactions, in which prior functionalization of the substrate with a metal-coordinating site was required, free primary, secondary, or tertiary hydroxy groups were found to be effective directing groups for the ortho-C–H palladation and subsequent olefination.

Key words

directing group - palladium catalysis - cross-coupling - C–H activation - arylethanols - acrylates

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References

References and Notes

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17 3-[2-(2-Hydroxyethyl)phenyl]acrylate Esters 3a–q; General Procedure A flame-dried 15 mL microwave vial containing a stirrer bar was charged with Pd(OAc)₂ (4.5 mg, 0.02 mmol, 10 mol%), N-acetylglycine (4.7 mg, 0.04 mmol, 20 mol%), and Ag₂CO₃ (82.7 mg, 150 mol%, 0.3 mmol). (F₃C)₂CHOH (1.0 mL), the appropriate alcohol 1 (0.4 mmol), and the appropriate acrylate 2 (0.2 mmol) were then added sequentially. The vial was sealed with a rubber septum and then degassed and backfilled with argon three times. Under a positive argon pressure, the vial was clamped and sealed with an aluminum cap equipped with a septum, then heated at 90 °C for 15 h. The solvent was removed under vacuum, and the product was purified by flash column chromatography. Butyl (2E)-3-[2-(2-Hydroxyethyl)phenyl]acrylate (3a) Purified by flash column chromatography (silica gel, 15% EtOAc–hexanes) as a colorless oil; yield: 29.8 mg (60%). ¹H NMR (400 MHz, CDCl₃): δ = 8.02 (d, J = 15.8 Hz, 1 H), 7.60 (dd, J = 5.5, 3.2 Hz, 1 H), 7.44–7.16 (m, 4 H), 6.38 (d, J = 15.8 Hz, 1 H), 4.22 (t, J = 6.7 Hz, 2 H), 3.83 (d, J = 4.3 Hz, 2 H), 3.05 (t, J = 6.8 Hz, 2 H), 1.70 (dt, J = 14.6, 6.8 Hz, 2 H), 1.50–1.38 (m, 2 H), 0.97 (t, J = 7.4 Hz, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 167.46, 142.20, 138.39, 133.94, 131.16, 130.42, 127.44, 127.12, 120.25, 64.86, 63.67, 36.78, 31.08, 19.53, 14.08. HRMS (APCI): m/z [M + Na]⁺ calcd for C₁₅H₂₀NaO₃: 271.1305; found: 271.1308.

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