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A 1,1-Carboboration Route to Bora-Nazarov Systems
Fang Ge1, Fatma Türkyilmaz1, Constantin G Daniliuc1
1Organisch-Chemisches Institut, Universität Münster, Corrensstrasse 40, 48149, Münster, Germany.
Abstract:
Hydroboration of the conjugated enynes 1 a and 1 b with Piers' borane [HB(C6F5)2] gave the respective dienylboranes trans-2 c and trans-2 d. Their photolysis resulted in the formation of the dihydroborole products 3 c and 3 d. Both were converted to their pyridine adducts 5 c and 5 d, respectively. Compounds 3 c and 5 c,d were characterized by X-ray diffraction. The reaction of the bis(enynyl)boranes 6 a and 6 b with B(C6F5)3 resulted in the formation of the dihydroboroles 7 a and 7 b, respectively. This reaction is thought to proceed by 1,1-carboboration of one of the enynyl substituents at boron to generate the dienylborane intermediates 8 a/8 b, followed by thermally induced bora-Nazarov ring-closure and subsequent stabilizing 1,2-pentafluorophenyl group migration from boron to carbon. Compound 7 a was characterized by X-ray diffraction and solid-state (11)B NMR spectroscopy.
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