C–C σ-Bond Oxidative Addition and Hydrofunctionalization by a Macrocycle-Supported Diiron Complex
C–C σ-Bond Oxidative Addition and Hydrofunctionalization by a Macrocycle-Supported Diiron Complex
复制标题
大环支持的二铁配合物的 C−C−键氧化加成和氢官能化
DOI：
10.1021/jacs.2c06266
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发表时间：
2022
影响因子：
15
通讯作者：
Tomson, Neil C.
中科院分区：
文献类型：
--
作者：
Liu, Tianchang;Murphy, Ryan P.;Carroll, Patrick J.;Gau, Michael R.;Tomson, Neil C.
本报告描述了第一个无辅助的C（sp）-C（sp 2）和C（sp）-C（sp 3）键氧化加成反应的例子，得到了化学上有利的产品。以（3 PDI 2）Fe 2（μ-N2）（PPh 3）2（[Fe 2N 2]0）为配体，配体为双铁配合物，与4，4 ′-二取代二苯乙炔（ArX-C = C-ArX; X = OMe，H，F，CF 3）反应，生成C（sp）-C（sp2）键氧化加成产物.当Ph-C_（sp）C-R底物用作底物（R = Me，Et，iPr，tBu）时，得到C（sp）-C（sp2）或C（sp）-C（sp3）键活化的产物，空间位阻较小的炔只经历C（sp）-C（sp3）键活化。用H2或HBpin处理C-C活化物种，发现形成C-C σ-键氢官能化产物。在氢化和硼氢化方案中，观察到二铁物质返回到[Fe 2N 2]0，从而完成C-C σ-键官能化的合成循环。
This report describes the first examples of unassisted C(sp)–C(sp2) and C(sp)–C(sp3) bond oxidative addition reactions to give thermodynamically favorable products. Treatment of a diiron complex supported by a geometrically and electronically flexible macrocyclic ligand, (3PDI2)Fe2(μ-N2)(PPh3)2([Fe2N2]0), with stoichiometric amounts of various 4,4′-disubstituted diphenylacetylenes (ArX–C≡C–ArX; X = OMe, H, F, CF3) yielded C(sp)–C(sp2) bond oxidative addition products. When Ph–C≡C–R substrates were used as substrates (R = Me, Et,iPr,tBu), products of either C(sp)–C(sp2) or C(sp)–C(sp3) bond activation were obtained, with the less sterically encumbering alkynes exclusively undergoing C(sp)–C(sp3) bond activation. Treatment of the C–C activation species with either H2or HBpin was found to form products of C–C σ-bond hydrofunctionalization. In both the hydrogenation and hydroboration schemes, the diiron species was observed to return to[Fe2N2]0, thereby completing synthetic cycles for C–C σ-bond functionalization.