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. 2008 Jul 9;130(27):8669-76.
doi: 10.1021/ja0774663. Epub 2008 Jun 13.

Amine-directed hydroboration: scope and limitations

Matthew Scheideman  1 , Guoqiang Wang, Edwin Vedejs
Affiliations

Amine-directed hydroboration: scope and limitations

Matthew Scheideman et al. J Am Chem Soc. .

Abstract

Iodine activation induces intramolecular hydroboration of homoallylic and bis-homoallylic amine boranes with good to excellent control of regiochemistry compared to control experiments using excess THF*BH 3. Deuterium labeling and other evidence confirm that the iodine-induced hydroboration reaction of homoallylic amine boranes occurs via an intramolecular mechanism equivalent to the classical 4-center process and without competing retro-hydroboration. Longer carbon chain tethers result in lower regioselectivity, whereas the shorter tether in allylic amines results in a switch to dominant intermolecular hydroboration. Regioselectivity in THF*BH 3 control experiments is higher for the allylic amine boranes compared to the iodine activation experiments, whereas the reverse is true for homoallylic amine borane activation.

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