The present report describes the X‐ray structural and theoretical studies of some new pinacolboronate esters, and it also outlines the use of the target structures in Suzuki coupling reactions to produce new aromatic or heteroaromatic esters and amides. X‐ray structural analysis of the studied compounds revealed that the pinacolborane ring's position with respect to the benzene ring varies, depending on the particular environment. An ortho‐positioned carboxylic ester (methyl ester) causes a nearly perpendicular orientation of the pinacolborane unit with respect to the benzene ring, whereas an ortho‐positioned amide (N,N‐dimethylamide) causes the pinacolborane unit to orient itself nearly coplanar. A plausible explanation has been provided, based on both steric and electronic factors.

The new cyclic boronic esters (III), (VIII), and (X) are prepared, their X‐ray‐structures are given and their conformations are discussed on the basis of theoretical calculations using the SHELXTL software.