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. 2011 Sep 7;133(35):13774-7.
doi: 10.1021/ja205912y. Epub 2011 Aug 10.

Pinene-derived iminodiacetic acid (PIDA): a powerful ligand for stereoselective synthesis and iterative cross-coupling of C(sp3) boronate building blocks

Junqi Li  1 , Martin D Burke
Affiliations
Free PMC article

Pinene-derived iminodiacetic acid (PIDA): a powerful ligand for stereoselective synthesis and iterative cross-coupling of C(sp3) boronate building blocks

Junqi Li et al. J Am Chem Soc. .
Free PMC article

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.

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