title: Pinene-derived iminodiacetic acid (PIDA): a powerful ligand for stereoselective synthesis and iterative cross-coupling of C(sp3) boronate building blocks.
abstract: Efficient access to chiral C(sp(3)) boronates in stereochemically pure form is critical for realizing the substantial potential of such building blocks in complex-molecule synthesis. We herein report that a pinene-derived iminodiacetic acid (PIDA) ligand enables the highly diastereoselective synthesis of a wide range of oxiranyl C(sp(3)) boronates from the corresponding olefins. These oxiranyl PIDA boronates, in turn, can be readily transformed into unprecedented stable α-boryl aldehydes via a novel 1,2-migration of the boronate group that proceeds with complete maintenance of stereochemical purity. B-Protected haloboronic acids containing dual sp(3)-hybridized C centers are readily accessible via this platform, and the herein demonstrated capacity for stereocontrolled iterative C(sp(3)) cross-coupling with this novel type of bifunctional reagent to access a medicinally important chiral small-molecule target in highly enantioenriched form represents a substantial advance for the building-block-based approach to synthesis.
authors.affiliation: Howard Hughes Medical Institute, Roger Adams Laboratory, Department of Chemistry, University of Illinois at Urbana-Champaign, 61801, USA.
authors.forename: Junqi
authors.initials: J
authors.lastname: Li
authors.forename: Martin D
authors.initials: MD
authors.lastname: Burke
mesh_terms: D000081008:Bicyclic Monoterpenes; D001897:Boronic Acids / Q000138:chemical synthesis / Q000737:chemistry*; D007098:Imino Acids / Q000138:chemical synthesis / Q000737:chemistry*; D008024:Ligands; D039821:Monoterpenes / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000081008:Bicyclic Monoterpenes; D001897:Boronic Acids; D007098:Imino Acids; D008024:Ligands; D039821:Monoterpenes; C005451:alpha-pinene; C008109:iminodiacetic acid