Synthesis of Ferrocene Derivatives with Planar Chirality via Palladium-Catalyzed Enantioselective C–H Bond Activation

Abstract

The first catalytic and enantioselective C-H direct acylation of ferrocene derivatives has been developed. A series of 2-acyl-1-dimethylaminomethylferrocenes with planar chirality were provided under highly efficient and concise one-pot conditions with up to 85% yield and 98% ee. The products obtained could be easily converted to various chiral ligands via diverse transformations.

Making Dimethylamino a Transformable Directing Group by Nickel‐Catalyzed CN Borylation

“…[2][3][4][5][6] In as imilar fashion, ar ange of transitionmetal-catalyzed CÀHf unctionalization reactions (DoCH) are knownt ob edirected by the Me 2 Ng roup. [7][8][9][10][11][12][13][14][15][16] More recently, ap alladium-catalyzed meta-selective aromatic CÀHf unctionalization( D mCH) employing the Me 2 Ng roup as ad irecting grouph as been reported by the Dong group. [17] While the repertoire of Me 2 N-directed reactions is growinga tar apid pace, the lack of ag eneral method to transform this group into otherf unctionalities hampers its wider application in organic synthesis.…”

Acylation of (Hetero)Arenes through CH Activation with Aroyl Surrogates

“…In the presence of palladium acetate and TBHP, good yields of the desired ketones were obtained with good selectivity (Scheme ). Later on, this aroyl source was also applied in the acylation of ferrocene derivatives 63a. Remarkably, the reaction could be performed in an enantioselective manner.…”

ChemInform Abstract: Synthesis of Planar Chiral Ferrocenes by Transition‐Metal‐Catalyzed Enantioselective C—H Activation

“…In 2014, Cui, Wu, and co-workers furthere xtended the directed enantioselective ferrocene CÀHa ctivation and achieved ap alladium-catalyzed enantioselective CÀHa cylation of dimethylaminomethylferrocene with 1,2-diketones (Scheme 4). [14] Commercially availableA c-l-Phe-OHw as used as the optimal ligand.P lanar chiral ferrocenyl ketones were synthesized under mild conditions with up to 85 %y ield and 98 % ee.I ng eneral, diaryl-substituted 1,2-diketones gave better yield ande nantioselectivity than dialkyl-substituted1 ,2-diketones. The product could be furthert ransformed into au seful planar chiral amino alcohol ligand efficiently.…”