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Tetrabutylammonium Fluoride Promoted Novel Reactions of o-Carborane: Inter- and Intramolecular Additions to Aldehydes and Ketones and Annulation via Enals and Enones
journal contribution
posted on 1998-01-30, 00:00 authored by Hiroyuki Nakamura, Kouichi Aoyagi, Yoshinori YamamotoThe addition of o-carborane (1) to
aldehydes 2 proceeded very smoothly in the presence of
aqueous
tetrabutylammonium fluoride (TBAF; 3 equiv) at room temperature, giving
the corresponding carbinols 3 in
high yields. The TBAF-mediated reaction was applied to the
intramolecular cycloaddition of o-carboranyl
aldehydes and ketones 4, and the corresponding five-, six-,
and seven-membered carboracycles were obtained
in good-to-high yields. Further, [3 + 2] annulation
between o-carborane (dianionic C2 synthons) and
α,β-unsaturated aldehydes and ketones (dicationic C3 synthons)
proceeded very smoothly in the presence of TBAF
to give the corresponding five-membered carbocycles in good-to-high
yields. Detailed mechanistic studies
revealed that the [3 + 2] annulation proceeded through kinetically
controlled 1,2-addition and thermodynamically
controlled 1,4-addition.