Deuterium-Labeling Studies on the C–H/Olefin Coupling of Aromatic Ketones Catalyzed by Fe(PMe3)4

Deuterium-labeling experiments were performed for the Fe(PMe3)4-catalyzed C–H/olefin coupling using a deuterium-labeled aromatic ketone with various alkenes. While the reactions with a variety of alkenes provided the linear alkylation products formed via 1,2-insertion of alkene into an Fe–H bond, the reversible 2,1-insertion proceeded during the reaction highly depends on the choice of the alkene. No H/D scrambling resulting from 2,1-insertion/β-elimination was detected for the reactions with a vinylsilane and N-vinylcarbazole, but the reactions­ with styrenes are considered to involve rapid 2,1-insertion/ β-elimination processes to cause significant levels of H/D scrambling.

Ruthenium(II)-catalyzed C–H activation and (4+2) annulation of aromatic hydroxamic acid esters with allylic amides

A (4+2) annulation under Ru(II)-catalysis is reported using aromatic hydroxamic acid esters as oxidizing directing group and allylic amides as unactivated olefin coupling partners, delivering a wide variety of aminomethyl...

Development of a Simple Removable Aliphatic Template for Remote Meta-Selective C−H Functionalization: Experimental and Computational Studies

Herein, we have successfully unveiled a simple and inexpensive removable aliphatic template as an effective DG template in promoting remote <i>meta</i>-C−H olefination of arenes for the first time. Remarkably, the template was achieved in excellent yields in just two steps and without column chromatography purification. The protocol is an efficient, economical and practical approach in achieving <i>meta</i>-C−H olefination in good to excellent isolated yields and high levels of <i>meta</i>-selectivity under mild conditions. A wide variety of substituted arenes and olefin coupling partners are well tolerated in this reaction. Moreover, the aliphatic template is found to be advantageous due to its easy synthesis, easy installation/removal, and recycle. We believe that this strategy offers new opportunities for the future development of new DG templates to promote site-selective C−H functionalizations.

Development of a Simple Removable Aliphatic Template for Remote Meta-Selective C−H Functionalization: Experimental and Computational Studies

Herein, we have successfully unveiled a simple and inexpensive removable aliphatic template as an effective DG template in promoting remote <i>meta</i>-C−H olefination of arenes for the first time. Remarkably, the template was achieved in excellent yields in just two steps and without column chromatography purification. The protocol is an efficient, economical and practical approach in achieving <i>meta</i>-C−H olefination in good to excellent isolated yields and high levels of <i>meta</i>-selectivity under mild conditions. A wide variety of substituted arenes and olefin coupling partners are well tolerated in this reaction. Moreover, the aliphatic template is found to be advantageous due to its easy synthesis, easy installation/removal, and recycle. We believe that this strategy offers new opportunities for the future development of new DG templates to promote site-selective C−H functionalizations.

Biomimetic Synthesis of Hitorins A and B via an Intermolecular Alkoxy Radical-Olefin Coupling Cascade

A biomimetic synthesis of hitorins A and B was achieved based on our modified biosynthetic proposal. In our synthesis, a radical cascade reaction between an alkoxy radical, generated from a hydroperoxide, and a monoterpene (+)-sabinene renders the tetrahydrofuran ring of hitorins A and B. In addition, experimental results supported that the oxidative cleavage of the tetrasubstituted olefin in a key intermediate is via a radical oxidation cascade followed by a Grob fragmentation.<br>