Synthesis of Sulfonyl Azides via Lewis Base Activation of Sulfonyl Fluorides and Trimethylsilyl Azide

Andrew S. Barrow; John E. Moses

doi:10.1055/s-0035-1561626

Synlett, Inhaltsverzeichnis

Synlett 2016; 27(12): 1840-1843
DOI: 10.1055/s-0035-1561626

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Synthesis of Sulfonyl Azides via Lewis Base Activation of Sulfonyl Fluorides and Trimethylsilyl Azide

Andrew S. Barrow

School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK eMail: John.moses@nottingham.ac.uk

,

John E. Moses*

School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK eMail: John.moses@nottingham.ac.uk

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Abstract

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Abstract

A protocol for the efficient conversion of sulfonyl fluorides into sulfonyl azides through Lewis base activation is described. The in situ generated sulfonyl azides are efficient diazo-transfer agents, affording diazo compounds and primary azides in excellent yields.

Key words

sulfonyl azides - Lewis base - diazo-transfer - sulfonyl fluoride - SuFEx

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Referenzen

References and Notes
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There is literature precedent for the conversion of sulfonyl fluorides to sulfonyl azides using NaN₃ in MeCN on an extremely electrophilic substrate:

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Conversion of sulfonyl fluorides to sulfonyl azides using NaN₃ in wet acetone has been reported:

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23 We continued our studies with TMSN₃ over NaN₃ due to its convenient liquid form, although both are viable options.
24 Typical Procedure for the Synthesis of Compound 2a To a solution of 2-nitrobenzenesulfonyl fluoride (103 mg, 0.5 mmol) in MeCN (1 mL) was added DBU (22 μL, 0.15 mmol, 0.3 equiv) followed by TMSN₃ (50 μL, 0.375 mmol, 0.75 equiv). The resultant solution was stirred at room temperature for 15 min, then a further portion of TMSN₃ (50 μL, 0.375 mmol, 0.75 equiv) was added. The solution was stirred for a further 45 min, filtered through a silica plug, eluting with EtOAc (50 mL), and volatiles removed under reduced pressure to yield 2a as a white solid. (105 mg, 0.46 mmol, 92%). ¹H NMR (400 MHz, CDCl₃): δ = 8.49–8.46 (m, 2 H), 8.20–8.16 (m, 2 H). ¹³C NMR (101 MHz, CDCl₃): δ = 151.2, 143.7, 128.9, 124.9. IR (CHCl₃): 2134 cm^–1.
25 See the Supporting Information for more information.
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Zusatzmaterial

Supporting Information