Synlett 2016; 27(12): 1840-1843
DOI: 10.1055/s-0035-1561626
letter
© Georg Thieme Verlag Stuttgart · New York

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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Publikationsverlauf

Received: 25. Februar 2016

Accepted after revision: 01. April 2016

Publikationsdatum:
21.April 2016 (eFirst)

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.

Supporting Information

 
  • 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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