Michigan State University

Dow Agrosciences LLC

University of Michigan

Robert E Maleczka

Milton R Smith

Jossian Oppenheimer

Daniel Holmes

Dmitrijs Sabasovs

Edith Onyeozili

Ghayoor A Chotana

Hao Li

Feng Shi

Chathurika R K Jayasundara

Venkata A Kallepalli

Methods for the borylation of aromatic compounds using cobalt catalysts are provided.

Methods for producing borylated arenes

Methods for the selective borylation of arenes, including arenes substituted with an electron-withdrawing group (e.g., 1-chloro-3-fluoro-2-substituted benzenes) are provided. The methods can be used, in some embodiments, to efficiently and regioselectively prepare borylated arenes without the need for expensive cryogenic reaction conditions.

The disclosure is directed to diboron compounds, related methods of making, and related intermediate boron and diboron compounds used to make the same. The diboron compounds can be used as reagents to prepare chemical intermediates that are used in pharmaceutical, agrochemical, and specialty electronics industries. The disclosed processes and compounds provide simplified synthetic paths that significantly reduce steps, improve scalability, and minimize costs for producing the diboron reagents.

Synthetic methods for diboron reagents and related compounds

Process for the preparation of oxazole, imidazole, and pyraxole boryl compounds. The compounds are intermediates to functionalized compounds, both natural and synthetic which are cytotoxic, anticancer and antiviral agents.

Process for producing oxazole, imidazole, pyrrazole boryl compounds

A process for producing cyano substituted arene boranes is described. The compounds are useful intermediates to pharmaceutical compounds using the cyano group as a reactant.

Process for producing cyano substituted arene boranes and compounds

A process for producing organic substituted aromatic or heteroaromatic compounds including biaryl and biheteroaryl compounds in a two-step reaction. In the first step, the aromatic or heteroaromatic compound is borylated in a reaction comprising a borane or diborane reagent (any boron reagent where the boron reagent contains a B&#x2014;H, B&#x2014;B or B&#x2014;Si bond) and an iridium or rhodium catalytic complex. In the second step, a metal catalyst catalyzes the formation of the organic substituted aromatic or heteroaromatic compound from the borylated compound and an electrophile such as an aryl or organic halide, triflate (OSOCF), or nonaflate (OSOCF). The steps in the process can be performed in a single reaction vessel or in separate reaction vessels. The present invention also provides a process for synthesis of complex polyphenylenes starting from halogenated aromatic compounds.

Process for the catalytic synthesis of biaryls and polymers from aryl compounds

A process is described for synthesizing aminoarylboronic esters of the general formulawherein R, R, and Rare each an alkyl, aryl, vinyl, alkoxy, carboxylic esters, amides, or halogen; Ar is any variety of phenyl, naphthyl, anthracyl, heteroaryl; and Ris alkyl, hydrogen, or aryl. The aminoarylboronic esters are produced via the metal-catalyzed coupling of arylboronic esters of the general formulawherein R and Rare any non-interfering group and X is chloro, bromo, iodo, triflates, or nonaflates to amines (primary and secondary). In particular, a process is described for the synthesis of the aminoarylboronic esters via a step-wise or tandem process in which one catalytic event is a metal-catalyzed borylation and the other catalytic event is a metal-catalyzed amination.

Synthesis of aminoarylboronic esters and substituted anilines from arenes via catalytic C-H activation/borylation/amination and uses thereof

A process to synthesize substituted phenols such as those of the general formula RR&prime;R&Prime;Ar(OH) wherein R, R&prime;, and R&Prime; are each independently hydrogen or any group which does not interfere in the process for synthesizing the substituted phenol including, but not limited to, halo, alkyl, alkoxy, carboxylic ester, amine, amide; and Ar is any variety of aryl or hetroaryl by means of oxidation of substituted arylboronic esters is described. In particular, a metal-catalyzed C&mdash;H activation/borylation reaction is described, which when followed by direct oxidation in a single or separate reaction vessel affords phenols without the need for any intermediate manipulations. More particularly, a process wherein Ir-catalyzed borylation of arenes using pinacolborane (HBPin) followed by oxidation of the intermediate arylboronic ester by OXONE is described.

Growing community of inventors

DeWitt, MI, United States of America

Robert E Maleczka