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DOI: 10.1055/s-2004-829165
Preparation of (E)-1-Alkenylboronic Acid Pinacol Esters via Transfer of Alkenyl Group from Boron to Boron
Publication History
Publication Date:
22 July 2004 (online)
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Abstract
Two synthetic routes to (E)-1-alkenylboronic acid pinacol esters 3 were investigated. Hydroboration of 1-alkynes 1 with 1,3,2-benzodioxaborole (catecholborane), in situ generated by the reaction of BH3 in THF with catechol, proceeded in the presence of a catalytic amount of dicyclohexylborane in THF at room temperature to give the corresponding (E)-1-alkenylboronic acid catechol esters 2. Treatment of the resultant esters 2 with 2,3-dimethyl-2,3-butanediol (pinacol) easily afforded the desired products 3, which are insensitive to air, moisture and chromatography, in good to high overall yields. The sequential reaction is a highly efficient route to 3 from BH3 in THF in a one-pot manner. Alternatively, hydroboration of 1 with 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (pinacolborane) was achieved in the presence of a catalytic amount of dicyclohexylborane at room temperature under neat conditions to afford the corresponding products 3 directly in good to excellent yields. This route is extremely efficient and environmentally benign from the viewpoints of making good use of pinacolborane and of using no solvent, and is capable of using a variety of alkynes 1 including functionalized ones such as HCCCH2Cl and HCCCH2OTHP.
Key words
(E)-1-alkenylboronic acid pinacol ester - 1-alkyne - dicyclohexylborane - catecholborane - pinacolborane
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References
There is a characteristic odor of dimethyl sulfide in the syringe used for removing the pinacolborane.
26We were aware of the fact that both Me2S-free and Me2S-containing pinacolborane were commercially available. This prompted us to examine the dicyclohexylborane-mediated hydroboration of 1b with Me2S-free pinacolborane, and thus 3b was obtained in 77% yield under the same reaction conditions, except for the reaction time (18 h).
27Dicyclohexylborane was used as a suspension in THF, and thus THF must be removed under reduced pressure in order to get dicyclohexylborane neat. If the residue, obtained by removal of THF, is a white solid, the hydroboration with pinacolborane will proceed without any trouble. But if the residue is viscous liquid, the hydroboration will scarcely proceed.
32The other alkenyl carbon atom was not observed. For example, see: refs. [5] [10]