当使用Ir[dF(CF3)ppy]2(dtbbpy)PF6 (1 mol%)为光敏剂、NiCl2•DME(10 mol%)为催化剂、4,4'-二叔丁基联吡啶(dtbbpy) (15 mol%)为配体,同时添加1.5当量的2,6-二甲基吡啶作为碱,在蓝光照射下能以优异的产率(83%)和E-选择性(88%)得到目标芳基化产物。对照实验表明,光照、配体、碱、镍催化剂...
Preliminary mechanistic inquiry suggests that boron stabilization provided by the hemilabile phosphoramidate ligand provides a -BH···[Ir] coordinated intermediate, which succumbs to borane-induced C(sp3)H bond activation.doi:10.1002/ejic.201601518Marcus W. Drover...
c ( sp 3 ) -h 键的立体选择性芳基化. 图 1. 研究背景与反应设计 ( 图片来源: nat.commun. ) 作者首先以烯醇硅醚 1 和 4-溴苯甲酸甲酯 2 为模板底物,对反应条件进行了详细优化(图2 ) .当使用 ir[df ( cf 3 ) ...
基于对该反应的深入认识,Tomislav Rovis和Robert Knowles都提出了利用磷酸盐与N-H作用,采用光氧化还原的策略,实现N-H键的断裂生成N自由基,随后发生1,5-氢迁移及与烯烃反应的过程(Scheme 1c)。 两位教授对自己的设计提出如下近似的机理(Scheme 2):光敏剂Ir(III)在光照作用下,生成激发态的Ir(III)*。与此同时,...
Jun课题组和Murai课题组分别报道了Ru催化的2-(N-烷基)氨基-吡啶的C(sp3)-H键烷基化反应;Shibata等人也报道了Ir/手性膦催化2-(N-烷基)氨基-吡啶分子中二级C(sp3)-H键的不对称烷基化反应。最近,来自京都大学的Yorimitsu课题组报道了Ir催化的末端烯烃与脲的C(sp3)-H键氢化-烷基化反应。
The selective formation of carbon–carbon bond by functionalization of an sp 3 C–H bond is still a challenge in organic synthesis. There are already examples involving transition metal catalysis. In this chapter we review the use of ruthenium(0) and ruthenium(II) catalysts for the formation of...
257R22M2MH2R2olefinmetathesisRRH2CCH22M2MH2RRH3CCH3IrOOPR2PR2LIrPR2PR2LMoNCHC(CH3)2PhiPrPri(CH3)(CF3)2CO(CH3)(CF3)2COR=t-Bu,L=C2H4,H2151617(C5Me5)(PMe3)IrH2hvC6H12(C5Me5)(PMe3)Ir(C5Me5)(PMe3)IrHCp(PMe3)IrH2hvC5H12Cp(PMe3)Ir(C5Me5)(PMe3)IrC5H11HR.G.Bergmaneta...
An efficient method for the oxidation of benzylic sp3 C–H bond to produce ketones or esters using rhenium(V) complexes as catalysts has been developed. Moreover, the amination of benzylic sp3 C–H bond with NH2Ts in the presence of NBS has also been reported in moderate to good yields ...
An Iridium/ketone dual catalysis pathway has been proposed (Fig.4c). The condensation of alkyl amine1with diazafluorenone4yields imine18, which is deprotonated at the α C−H bond to form 2-azaallyl anion1949. The delocalized carbanion19then undergoes asymmetric addition at the diazafluorenyl...
C-H functionalizationnitrenoidenantioselectiverutheniumchiral-at-metalTransition﹎etal nitrenoids are well〆stablished for their CH amination chemistry but this work demonstrates that N゛cylnitrenoids can surprisingly undergo C(sp)–H oxygenations instead, even in an enantioselective fashion. Abstract This ...