Polyborylated-alkenes are valuable polymetalloid reagents in modern organic synthesis, providing access to a wide array of transformations, including the construction of multiple C–C and C–heteroatom bonds. However, because they contain similar boryl groups, many times their transformation faces the main challenge in controlling the chemo-, regio- and stereoselectivity. One way to overcome these limitations is by installing different boron groups that can provide an opportunity to tune their reactivity toward better chemo-, regio- and stereoselectivity. Yet, the preparation of polyborylated-alkenes containing different boryl groups has been rare. Herein we report concise, highly site-selective, and stereoselective boron-masking strategies of polyborylated alkenes. This is achieved by designed stereoselective trifluorination and MIDA-ation reactions of readily available starting polyborylated alkenes. Additionally, the trifluoroborylated-alkenes undergo a stereospecific interconversion to Bdan-alkenes. These transition-metal free reactions provide a general and efficient method for the conversion of polyborylated alkenes to access 1,1-di-, 1,2-di-, 1,1,2-tris-(borylated) alkenes containing BF3M, Bdan, and BMIDA, a family of compounds that currently lack efficient synthetic access. Moreover, tetraborylethene undergoes the metal-free MIDA-ation reaction to provide the mono BMIDA tetraboryl alkene selectively. The mixed polyborylalkenes are then demonstrated to be useful in selective C–C and C–heteroatom bond-forming reactions. Given its simplicity and versatility, these stereoselective boron-masking approaches hold great promise for organoboron synthesis and will result in more transformations.
Bibliographical noteFunding Information:
This research was supported by grants from The U.S.-Israel Binational Science Foundation (Grant No. 2020033) and the Israel Science Foundation (Grant No. 287/21) to A.M. We thank Dr. Benny Bogoslavsky (The Hebrew University of Jerusalem, Israel) for the X-ray structure determination. N.H., are grateful for a fellowship from The Hebrew University of Jerusalem. N.E. is thankful for a Ph.D. fellowship from the Neubauer Foundation. We are grateful to Professor Gary Molander (University of Pennsylvania) for useful discussions. This Article is dedicated to Professor Ilan Marek on the occasion of his 60th birthday.
© 2023, The Author(s).