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. 2020 Feb 21;22(4):1665-1669.
doi: 10.1021/acs.orglett.0c00267. Epub 2020 Feb 4.

Safety Assessment of Benzyne Generation from a Silyl Triflate Precursor

Andrew V Kelleghan  1 , Carl A Busacca  2 , Max Sarvestani  2 , Ivan Volchkov  2 , Jose M Medina  1 , Neil K Garg  1
Affiliations

Safety Assessment of Benzyne Generation from a Silyl Triflate Precursor

Andrew V Kelleghan et al. Org Lett. .

Abstract

Silyl triflate precursors to benzyne and related intermediates have emerged as valuable synthetic building blocks. However, data addressing the safety of employing these silyl triflate precursors are lacking. We report the calorimetric analysis of a typical Kobayashi procedure for forming and trapping benzyne using a silyl triflate precursor. Our findings suggest that, unlike benzenediazonium carboxylate precursors to benzyne, silyl triflates may be employed under mild conditions without severe concern for runaway reaction.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1.
Figure 1.
Strategies for benzyne formation and select synthetic applications.
Figure 2.
Figure 2.
Representative benzyne reaction investigated in our calorimetric study.
Figure 3.
Figure 3.
Self-heat rate (dT/dt) vs temperature data obtained from ARSST calorimetry performed on samples taken from the reaction (see Figure 2) mixture directly after adding all reagents. No exotherms were observed. Full data sets for all experiments are located in the SI.
Figure 4.
Figure 4.
Pressure-rise rate (dP/dt) vs temperature data obtained from ARSST calorimetry performed on samples taken from the reaction (see Figure 2) mixture directly after adding all reagents. Negligible buildup of pressure was observed. Full data sets for all experiments are located in the SI.
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