Oxidative Coupling with Zr(IV) Supported by a Noninnocent Anthracene-Based Ligand: Application to the Catalytic Cotrimerization of Alkynes and Nitriles to Pyrimidines.
Oxidative Coupling with Zr(IV) Supported by a Noninnocent Anthracene-Based Ligand: Application to the Catalytic Cotrimerization of Alkynes and Nitriles to Pyrimidines.
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DOI：
10.1021/jacs.8b07418
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发表时间：
2018-09-26
影响因子：
15
通讯作者：
Agapie T
中科院分区：
文献类型：
--
作者：
Low CH;Rosenberg JN;Lopez MA;Agapie T
本文报道了以9，10-蒽二基联双酚氧配体L. ZrIVLBn 2（1）经历容易的光解还原，伴随着联苄基和ZrIVL（THF）3（2）的形成，其显示出双电子还原的蒽部分。利用配体存储的还原当量，2促进内部和终端炔的氧化偶联到isolable zirconacyclopentadiene配合物，证明了可逆利用蒽作为氧化还原水库。与二苯基乙炔在CO下，按化学计量形成环己烯酮。2是胜任催化形成嘧啶从炔和腈。机理研究表明，对嘧啶的选择性源于优选形成的azazirconacyclopentadiene中间体，该中间体优先与腈反应而不是与炔反应。
We report the synthesis and reactivity of Zr complexes supported by a 9,10-anthracenediyl-linked bisphenoxide ligand, L. ZrIVLBn2 (1) undergoes facile photolytic reduction with concomitant formation of bibenzyl and ZrIVL(THF)3 (2), which displays a two-electron reduced anthracene moiety. Leveraging ligand-stored reducing equivalents, 2 promotes the oxidative coupling of internal and terminal alkynes to isolable zirconacyclopentadiene complexes, demonstrating the reversible utilization of anthracene as a redox reservoir. With diphenylacetylene under CO, cyclopentadienone is formed stoichiometrically. 2 is competent for the catalytic formation of pyrimidines from alkynes and nitriles. Mechanistic studies suggest that selectivity for pyrimidine originates from preferred formation of an azazirconacyclopentadiene intermediate, which reacts preferentially with nitriles over alkynes.
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影响因子：
15
作者：
Blackmore, Karen J.;Lal, Neetu;Heyduk, Alan F.
通讯作者：
Heyduk, Alan F.
影响因子：
18.3
作者：
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通讯作者：
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影响因子：
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作者：
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作者：
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通讯作者：
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