California Institute of Technology

Wenbo Liu

Robert H Grubbs

Brian M Stoltz

Anton A Toutov

Kerry N Betz

Alexey Fedorov

David P Schuman

The present disclosure describes methods for silylating aromatic derivatives, comprising the use of hydrosilanes and potassium hydroxide.

Silylated derivatives of aromatic heterocycles

The present invention is directed to compositions for silylating organic substrates containing C&#x2014;H or O&#x2014;H bonds, especially heteroaromatic substrates. The compositions are derived from the preconditioning of mixtures of hydrosilanes or organodisilanes with bases, including metal hydroxide and metal alkoxide bases. In some embodiments, the preconditioning results in the formation of reactive silicon hydride species.

Stable silylating reagents

The present disclosure describes methods for silylating heteroaromatic derivatives, comprising the use of hydrosilanes and potassium hydroxide.

The present disclosure describes novel silylated heteroaromatic derivatives, including those prepared by methods comprising the use of hydrosilanes and at least one strong base, the definition of strong base now also including hydroxide, especially KOH.

The present invention describes chemical systems and methods for silylating N&#x2014;H bonds of aliphatic amines, said system or method comprising or consisting essentially of a mixture of (a) at least one organosilane and (b) at least one hydroxide, especially KOH, said system being preferably, but not necessarily substantially free of a transition-metal compound, and said methods comprising contacting a quantity of the organic substrate with a mixture of (a) at least one organosilane and (b) at least one strong base, under conditions sufficient to replace an N&#x2014;H bond with a silyl N&#x2014;Si bond.

Preparation of silylamines by the dehydrogeative coupling of N&#x2014;H and Si&#x2014;H bonds

The present invention is directed to a mild, efficient, and general direct C(sp)-H bond silylation. Various embodiments includes methods, each method comprising or consisting essentially of contacting at least one organic substrate comprising a terminal alkynyl C&#x2014;H bond, with a mixture of at least one organosilane and an alkali metal hydroxide, alkali metal alkoxide, or alkali metal hydride under conditions sufficient to form a silylated terminal alkynyl moiety. The methods are operable in the presence or substantially absence of transition-metal compounds. The systems associated with these methods are also disclosed.

Base-catalyzed silylation of terminal alkyne C&#x2014;H bonds

The present invention is directed to a mild, efficient, and general direct C(sp)-H bond silylation of terminal olefins. Various embodiments includes methods, each method comprising or consisting essentially of contacting at least one organic substrate comprising a terminal olefinic C&#x2014;H bond, with a mixture of at least one organosilane, organosilane, or mixture thereof and an alkali metal alkoxide or alkali metal hydroxide, such that the contacting results in the formation of a silylated olefinic product. The systems associated with these methods are also disclosed.

Base-catalyzed silylation of terminal olefinic C&#x2014;H bonds

The present invention describes chemical systems and methods for silylating aromatic organic substrates, said system or method comprising or consisting essentially of a mixture of (a) at least one organosilane and (b) at least one strong base, the definition of strong base now also including KOH, said system being preferably, but not necessarily substantially free of a transition-metal compound, and said methods comprising contacting a quantity of the organic substrate with a mixture of (a) at least one organosilane and (b) at least one strong base, under conditions sufficient to silylate the aromatic substrate.

Silylation of aromatic heterocycles by earth abundant transition-metal-free catalysts

The present invention describes chemical systems and methods for silylating heteroaromatic organic substrates using at least alkoxide base, preferably a potassium alkoxide base and at least one organodisilane and (b) at least one alkoxide base. Both methods and compositions for affecting these transformations are disclosed.

Silylation of aromatic heterocycles by disilanes using potassium alkoxide catalysts

The present invention is directed to a mild, efficient, and general direct C(sp)-H bond silylation. Various embodiments includes methods, each method comprising or consisting essentially of contacting at least one organic substrate comprising a terminal alkynyl C&#x2014;H bond, with a mixture of at least one organosilane and an alkali metal hydroxide, under conditions sufficient to form a silylated terminal alkynyl moiety. The methods are operable in the substantially absence of transition-metal compounds. The systems associated with these methods are also disclosed.

The present invention describes chemical systems and methods for silylating heteroaromatic organic substrates, said system consisting essentially of a mixture of (a) at least one organodisilane and (b) at least alkoxide base, preferably a potassium alkoxide base, and said methods comprising contacting a quantity of the organic substrate with a mixture consisting essentially of (a) at least one organodisilane and (b) at least one alkoxide base, preferably a potassium alkoxide, under conditions sufficient to silylate the heteroaromatic substrate.

Growing community of inventors

Pasadena, CA, United States of America

Wenbo Liu