The stereoselective synthesis of alkylboronic esters from vinyl iodides and various nucleophiles, alkenes or alkynes is presented. Reactions proceed through hydroborations and 1,2-metallate rearrangements without any transition metal catalyst.
Pd-catalyzed borylation of phenols via SO2F2 activation is presented for the synthesis of aryl/heteroaryl boronic esters, selected drug molecules and natural product derivatives as well as a novel boronate-based fluorescent probe HTCPB.
The synthesis of 3,3-substituted alkenyl oxindole boronates and tetrasubstituted β-borylesters and β-borylamides was achieved via a transition metal-free carbonyl-directed boron-Wittig reaction of α-bis(boryl)carbanions, which is difficult to achieve via other known methods.
The Matteson homologation is found to be a versatile tool for the stereoselective synthesis of polyunsaturated alkyl boronic esters, which can be used for the construction of five- and six-membered carbocycles via ring-closing metathesis.
An ionic liquid-catalyzed metal-free approach was proposed to upcycle waste PET into dimethyl terephthalate and boronic esters, facilitated by multiple hydrogen bonds.