Photocatalytic Desulfonylative Homocoupling of Benzylic Sulfone Derivatives

Ryusei Ohkura; Motoo Ohtsuka; Jacky C.-H. Yim; Masakazu Nambo; Cathleen M. Crudden

doi:10.1055/a-1942-5695

Synlett, Table of Contents

Synlett 2023; 34(01): 81-85
DOI: 10.1055/a-1942-5695

letter

Special Edition Thieme Chemistry Journals Awardees 2022

Photocatalytic Desulfonylative Homocoupling of Benzylic Sulfone Derivatives

Ryusei Ohkura

^aDepartment of Chemistry, Graduate School of Science, Nagoya University, Chikusa, Nagoya, 464-8602, Japan

,

Motoo Ohtsuka

^bInstitute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Chikusa, Nagoya, 464-8602, Japan

,

Jacky C.-H. Yim

^bInstitute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Chikusa, Nagoya, 464-8602, Japan

,

Masakazu Nambo ∗

^aDepartment of Chemistry, Graduate School of Science, Nagoya University, Chikusa, Nagoya, 464-8602, Japan

^bInstitute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Chikusa, Nagoya, 464-8602, Japan

,

Cathleen M. Crudden∗

^bInstitute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Chikusa, Nagoya, 464-8602, Japan

^cQueen's University, Department of Chemistry, Chernoff Hall, Kingston, Ontario, K7L 3N6, Canada

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Abstract

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Abstract

A desulfonylative homocoupling of benzylic sulfone derivatives through a photoredox Ir catalyst is described. The 3,5-bis(trifluoromethyl)phenyl group is an effective substituent on sulfonyl group in this reaction, providing the structurally diverse multiply arylated ethanes in good yields. The α-deuterated or α-fluorinated sulfones, which can be readily prepared by α-functionalization, were also applicable, highlighting an avenue to synthesize medicinally important structures.

Key words

desulfonylative homocoupling - sulfone - photoredox catalysis - multiply arylated alkanes - carbon–sulfonyl bond activation

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References

References and Notes

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16 Procedure for Desulfonylative Homocoupling of Benzhydryl Sulfone 6a A 10 mL sealable reaction tube equipped with a magnetic stirring bar and a septum was evacuated, flame-dried under vacuum, cooled to room temperature, and backfilled with Ar. To the glass vessel were added benzhydryl 3,5-bis(trifluoromethyl)phenyl sulfone (6a, 133 mg, 0.3 mmol) and Ir(ppy)₃ (2.0 mg, 0.003 mmol). The mixture was evacuated under vacuum and refilled with Ar. This cycle was repeated two additional times. Under an Ar atmosphere, acetone (1.5 mL), degassed H₂O (0.15 mL), and i-Pr₂NEt (105 μL, 0.6 mmol) were added, and the reaction was sealed and stirred under irradiation (Kessil^® PR 160, 456 nm) for 17 h. The solvent was removed under reduced pressure and diluted with EtOAc. The mixture was passed through a pad of silica gel with copious washings with EtOAc (ca. 50 mL). The filtrate was concentrated under reduced pressure. The crude product was purified by PTLC (EtOAc–Hex = 1:100 to 1:50) to afford 1,1,2,2-tetraphenylethane (7a, 48.0 mg, 96%) as a white solid. ¹H NMR (400 MHz, CDCl₃): δ = 4.77 (s, 2 H), 6.99–7.03(m, 4 H), 7.09–7.17 (m, 16 H). ¹³C NMR (150 MHz, CDCl₃): δ = 56.3, 125.8, 128.1, 128.5, 127.4, 143.4. HRMS (DART) m/z calcd for C₂₆H₂₁ [M – H]⁺: 333.1643; found: 333.1637.

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