Alkynylboration products

Reaction of (diisopropylamino)chloroboryl ethers of alkynols (57) with alkynyl-stannanes (58) in the presence of nickel catalysts has been reported to afford formal f/ms-alkynylboration products (60), which could undergo the Suzuki-Miyaura coupling with organic halides. The 2-borylalkenylnickel(II) complex (59) was isolated as an intermediate in a reaction of the chloroboryl ether (57) with 1 equiv. of a nickel(0)-phosphine complex and characterized by X-ray crystallography.61... 

Various electrophiles other than iodine have been used to induce alkenyl coupling (9). Alkyl haUdes and protic acids react with alkynylborates to yield mixtures of stereoisomeric alkenylboranes. Nevertheless, oxidation of these products is synthetically useful, providing single ketones (296—298). Alcohols are obtained from the corresponding alkenylborates. 

Among nucleophiles used are enols " (including mono- and bis-TMS ethers, which are particularly favorable ) derivatives of P N and S in hydrogen sulfite dithionate and sulfide Si, Ge, Sn and alkyl or aryl in derivatives of Cd, Zn or Li . The Li reagents in particular require special experimental conditions, including dichloro methane as solvent and radical scavengers. Many nucleophiles cause electron addition to the cations, with formation of radicals. Aromatic substitutions displace not only H but SnMej or SiMe3 . Allylsilanes and trialkyl alkynylborates provide synthetically useful products. 

Even in the alkynyl-aryl coupling where Zn, B, Sn, and Mg have been shown to be comparably satisfactory in less demanding cases, some clear-cut differences have been shown in more demanding cases (Scheme 5). This aspect is further discussed in Sect. III.2.8.2. Curiously, ethynylborates do not give the desired products in any detectable amount, even though higher alkynylborates react satisfactorily. 

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