Disclosed are compounds of the formula: ##STR00001##
and the respective enantiomers, stereochemical isomers, hydrates, solvates, tautomers and pharmaceutically acceptable salts of such compounds; which can be useful in the treatment of various types of cancer.

Provided herein are 19-nor C3,3-disubstituted steroids of Formula (I):

##STR00001##

and pharmaceutically acceptable salts thereof; wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are as defined herein, and A is a heteroaryl ring system comprising 3 or 4 nitrogens as defined herein. Such compounds are contemplated useful for the prevention and treatment of a variety of CNS-related conditions, for example, treatment of sleep disorders, mood disorders, schizophrenia spectrum disorders, convulsive disorders, disorders of memory and/or cognition, movement disorders, personality disorders, autism spectrum disorders, pain, traumatic brain injury, vascular diseases, substance abuse disorders and/or withdrawal syndromes, and tinnitus.

Provided herein are 19-nor C3,3-disubstituted C21-pyrazolyl steroids of Formula (I):

##STR00001##

and pharmaceutically acceptable salts thereof; wherein , R.sup.1, R.sup.2, R.sup.3a, R.sup.3b, R.sup.4a, R.sup.4b, R.sup.5, R.sup.6, and R.sup.7 are as defined herein. Such compounds are contemplated useful for the prevention and treatment of a variety of CNS-related conditions, for example, treatment of sleep disorders, mood disorders, schizophrenia spectrum disorders, convulsive disorders, disorders of memory and/or cognition, movement disorders, personality disorders, autism spectrum disorders, pain, traumatic brain injury, vascular diseases, substance abuse disorders and/or withdrawal syndromes, and tinnitus.

Methods of preparing fluorinated compounds by carboxylative fluorination using fluoride are contained herein. Fluorinated compounds are provided. Methods of using fluorinated compounds are contained herein.

A chemoselective and reactive Mn(CF.sub.3-PDP) catalyst system that enables for the first time the strategic advantages of late-stage aliphatic CH hydroxylation to be leveraged in aromatic compounds. This discovery will benefit small molecule therapeutics by enabling the rapid diversification of aromatic drugs and natural products and identification of their metabolites.

Methods of preparing fluorinated compounds by carboxylative fluorination using fluoride are contained herein. Fluorinated compounds are provided. Methods of using fluorinated compounds are contained herein.

Provided herein are 19-nor C3,3-disubstituted steroids of Formula (I):

##STR00001##

and pharmaceutically acceptable salts thereof; wherein , R.sup.1, R.sup.2, R.sup.3a, R.sup.3b, R.sup.4a, and R.sup.4b are as defined herein, and A is a carbon bound substituted or unsubstituted 5- to 6-membered heteroaryl ring as defined herein. Such compounds are contemplated useful for the prevention and treatment of a variety of CNS-related conditions, for example, treatment of sleep disorders, mood disorders, schizophrenia spectrum disorders, convulsive disorders, disorders of memory and/or cognition, movement disorders, personality disorders, autism spectrum disorders, pain, traumatic brain injury, vascular diseases, substance abuse disorders and/or withdrawal syndromes, and tinnitus.

Provided herein is a compound of Formula (I)

##STR00001##

or a pharmaceutically acceptable salt thereof, wherein R.sup.3a, R.sup.5, R.sup.6a, R.sup.6b, R.sup.17, R.sup.21a, R.sup.21b, R.sup.m, R.sup.n, R.sup.16a, R.sup.16b, R.sup.7a, R.sup.7b, R.sup.12a, R.sup.12b, R.sup.11a, R.sup.11b, R.sup.2a, R.sup.2b, R.sup.19, R.sup.4a, and R.sup.4b are defined herein. Also provided herein are pharmaceutical compositions comprising a compound of Formula (I) and methods of using the compounds, e.g., in the treatment of CNS-related disorders.

A method of reducing an aromatic ring or a cyclic, allylic ether in a compound includes preparing a reaction mixture including a compound including an aromatic moiety or a cyclic, allylic ether moiety, an alkali metal, and either ethylenediamine, diethylenetriamine, triethylenetetramine, or a combination thereof, in an ether solvent; and reacting the reaction mixture at from ?20? C. to 30? C. for a time sufficient to reduce a double bond in the aromatic moiety to a single bond or to reduce the cyclic, allylic ether moiety.

Provided herein are 19-nor C3, 3-disubstituted steroids of Formula (I): and pharmaceutically acceptable salts thereof; wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are as defined herein, and A is a heteroaryl ring system comprising 3 or 4 nitrogens as defined herein. Such compounds are contemplated useful for the prevention and treatment of a variety of CNS-related conditions, for example, treatment of sleep disorders, mood disorders, schizophrenia spectrum disorders, convulsive disorders, disorders of memory and/or cognition, movement disorders, personality disorders, autism spectrum disorders, pain, traumatic brain injury, vascular diseases, substance abuse disorders and/or withdrawal syndromes, and tinnitus.

##STR00001##