Boron insertion into alkyl ether bonds via zinc/nickel tandem catalysis
Boron insertion into alkyl ether bonds via zinc/nickel tandem catalysis
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DOI：
10.1126/science.abg5526
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发表时间：
2021-04-09
期刊：
影响因子：
56.9
通讯作者：
Dong, Guangbin
中科院分区：
文献类型：
--
作者：
Lyu, Hairong;Kevlishvili, Ilia;Dong, Guangbin
裂解烷基醚中的碳-氧（C-O）键的温和方法可以通过精心制作这些坚固的、容易获得的前体来简化化学合成。本文报道了在镍催化剂和锌还原剂存在下，二溴硼烷与烷基醚反应，将硼插入到C-O键中。随后的反应性可以实现环醚的氧氮取代或一碳同系化，并且更广泛地简化生物活性化合物的制备。机理研究揭示了通过锌/镍串联催化裂解然后反弹途径。
Mild methods to cleave the carbon-oxygen (C-O) bond in alkyl ethers could simplify chemical syntheses through the elaboration of these robust, readily available precursors. Here we report that dibromoboranes react with alkyl ethers in the presence of a nickel catalyst and zinc reductant to insert boron into the C-O bond. Subsequent reactivity can effect oxygen-to-nitrogen substitution or one-carbon homologation of cyclic ethers and more broadly streamline preparation of bioactive compounds. Mechanistic studies reveal a cleavage-then-rebound pathway via zinc/nickel tandem catalysis.