The invention generally relates to methods of making substituted arenes via direct C—H, C—O, C—S, or C—N bond conversion and methods of synthesizing isotopically-labeled substituted arenes via direct carbon-halogen bond conversion. The invention also relates to anaerobic catalyst systems comprising an acridinium photocatalyst and a nucleophile selected from a halide, a cyanide, and an isotopically-labeled amine. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present invention.

The subject invention provides synthetic compounds, and compound complexes having catalytic activities towards oxidation or oxygenation, and/or dehydrogenation of various substrates comprising C—H bonds. The catalysts of the subject invention comprise a dinuclear Cu(I)/Cu(II) center that can convert between a resting state and a reactive species. The subject invention also provides methods of using such catalysts for the oxidation of substrates comprising C—H bonds, e.g., hydrocarbons, to synthesize chemicals for use as pharmaceuticals and industrial feedstock.

Embodiments of the present disclosure provide for Rh(I) catalysts, methods of making alkenyl substituted arenes (e.g., allyl arene, vinyl arene, and the like), methods of making alkyl substituted arenes, and the like.

An oxidative homocoupling method of synthesizing certain 2,2′-bithiophenes from thiophenes using oxygen as the terminal oxidant is disclosed. In non-limiting examples, the method uses oxygen along with a catalytic system that includes palladium, an assistive ligand, and a non-palladium metal additive to catalyze one of the following reactions: ##STR00001## Associated catalytic systems and compositions are also disclosed.

Provided herein are a method of Ru(II)-catalyzed enantioselective synthesis of a cyclic compound and cyclic compounds formed therefrom. The method includes providing a precursor compound having an unfunctionalized C—H bond and activating the unfunctionalized C—H bond by reacting the precursor compound in the presence of co-catalysts including a Ru(II) arene complex and a chiral transient directing group (CTDG).

The subject invention provides synthetic compounds, and compound complexes having catalytic activities towards oxidation or oxygenation, and/or dehydrogenation of various substrates comprising C−H bonds. The catalysts of the subject invention comprise a dinuclear Cu(I)/Cu(II) center that can convert between a resting state and a reactive species. The subject invention also provides methods of using such catalysts for the oxidation of substrates comprising C−H bonds, e.g., hydrocarbons, to synthesize chemicals for use as pharmaceuticals and industrial feedstock.

A method for C—H bond activation and/or C—N coupling reaction comprises adding a hydrocarbon material to a container; adding a metal catalyst to the container; adding a primary or a secondary amine to the container. The metal catalyst is represented by the following formula:

##STR00001##

where Q is a 5 or 6 membered aromatic ring; W, X, and Y are the same or different, and are independently N, S, P, or O; M is Ni, Pd, Fe, Co, Cr, Mn, Cu, Pt, Ir, or Ru; Z is halide (F, Cl, Br, or I); R1 and R2 are the same or different, and are independently alkyl, aryl, alkylaryl or cycloalkyl; and n is 1, 2, or 3.

Provided are a 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-based monophosphine ligand and intermediates thereof, and preparation methods and uses of the same. The monophosphine ligand is a compound represented by formula I or formula I′, or an enantiomer, a raceme or a diastereoisomer thereof, including phosphonite ligands, phosphite ligands, phosphoramidite ester ligands, phosphoric acid and phosphonic amide. The monophosphine ligand is prepared with a known 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-7,7′-diol derivative as a raw material through a scheme in which the compound presented by formula II acts as an intermediate. The present disclosure provides a novel monophosphine ligand, which can be used as a ligand in a metal-catalysed organic reactions or in directly catalyzing an organic reaction, especially as a chiral monophosphine ligand widely used in many chiral catalytic reactions such as asymmetric addition, asymmetric hydrogenation, asymmetric coupling, and asymmetric allyl alkylation, having economic practicality and industrial application prospects. ##STR00001##

A method for C—H bond activation and/or C—N coupling reaction comprises using a metal catalyst to catalyze the C—H bond activation and/or C—N coupling reaction; wherein the metal catalyst represented by the following formula a metal catalyst for C—H bond activation and/or C—N coupling reaction, and a method using the same and application thereof. Specifically, a metal catalyst represented by the following formula: ##STR00001##
wherein Q is a 5 or 6 membered aromatic ring; W, X, and Y are the same or different, and are independently N, S, P, or O; M is Ni, Pd, Fe, Co, Cr, Mn, Cu, Pt, Ir, or Ru; Z is halide (F, Cl, Br, or I), acetate, water, or hydroxyl; R.sub.1 and R.sub.2 are the same or different, and are independently alkyl, aryl, alkylaryl or cycloalkyl.

Embodiments of the present disclosure provide for Rh(I) catalysts, methods of making alkenyl substituted arenes (e.g., allyl arene, vinyl arene, and the like), methods of making alkyl substituted arenes, and the like.