**4. Conclusions**

In conclusion, alkyne groups are not always compatible with traditional CHB conditions and direct synthesis of borylated aryl alkynes is challenging. However, taking advantage of the tolerance of aryl bromides toward CHB, we have developed an efficient one-pot aromatic C–H activation borylation/Sonogashira coupling protocol for the synthesis of borylated aromatic alkynes. This methodology tolerates a variety of functional groups and several borylated alkynes were prepared in good to high yields. Boronic esters as well as alkynes have a variety of applications in medicinal chemistry, polymers, material science, etc. Boronic esters can serve as sensors for carbohydrates, protecting groups for polymers and sugars, bioactive functional groups or versatile precursors for more complex molecules to name some applications [2]. Introduction of an alkyne functionality to the aromatic ring can extent conjugation and change electronic properties (e.g., fluorescence [40]) or geometrical features (e.g., crystal arrangements [38]) of the molecules. Taking advantage of both functionalities (alkyne and boronic ester) in the same ring can result in useful intermediates, we anticipate that our report will facilitate the synthesis of these compounds and the examination of their properties.

**Supplementary Materials:** The following are available online: Spectral data for the borylated products.

**Author Contributions:** Conceptualization of the work described herein was done by G.A.C., M.R.S.III, and R.E.M.J., G.A.C. developed the method, which was further optimized by S.L.M., J.R.M.B. contributed to the preparation and analysis of compounds 23 and 25. G.A.C. and J.R.M.B wrote the original draft, which was reviewed/edited by all authors. All authors have read and agreed to the published version of the manuscript.

**Funding:** This research was funded by the Michigan Technology Tri-Corridor Fund grant number GR-564 and the NIH grant number GM63188 (to M.R.S.III).

**Acknowledgments:** We thank Daniel Holmes and Feng Shi for helpful discussions.

**Conflicts of Interest:** The authors declare the following competing financial interest(s): S.L.M., M.R.S.III, and R.E.M.J. own a percentage of BoroPharm, Inc.
