Steroids: reactions and partial synthesis

The article reviews the progress in the chemistry of the steroids that was published between January and December, 2001. The reactions and partial syntheses of estrogens, androgens, pregnanes, cholic acid derivatives, cholestanes and vitamin D analogues are covered. There are 184 references.     

Steroids: reactions and partial synthesis

This article reviews the progress in the chemistry of the steroids that was published between January and December 2003. The reactions and partial synthesis of estrogens, androgens, pregnanes, cholic acid derivatives, cholestanes and vitamin D analogues are covered. There are 152 references.     

Steroids: reactions and partial synthesis

The article reviews the progress in the chemistry of the steroids that was published between January and December, 2000. The reactions and partial syntheses of estrogens, androgens, pregnanes, cholic acid derivatives, cholestanes and vitamin D analogues are covered. There are 169 references.     

Steroids: reactions and partial synthesis

The article reviews the progress in the chemistry of the steroids that was published between January and December 2002. The reactions and partial synthesis of estrogens, androgens, pregnanes, cholic acid derivatives, cholestanes and vitamin D analogues are covered. There are 160 references.     

Steroids: partial synthesis in medicinal chemistry

This article reviews the progress in the chemistry of the steroids that was published between January and December 2004. The reactions and partial synthesis of estrogens, androgens, pregnanes, cholic acid derivatives, cholestanes and vitamin D analogues are covered. There are 127 references.     

Steroids: partial synthesis in medicinal chemistry

This article reviews the progress in the chemistry of the steroids that was published between January and December 2005. The reactions and partial synthesis of estrogens, androgens, pregnanes, bile acid derivatives, cholestanes and vitamin D analogues are covered. There are 139 references.     

Steroids: partial synthesis in medicinal chemistry

This article reviews the progress in the chemistry of the steroids which was published between January and December 2006. The reactions and partial synthesis of estrogens, androgens, pregnanes, bile acid derivatives, cholestanes and vitamin D analogues are covered. There are 159 references.     

N-heterocyclic phosphenium cations: syntheses and cycloaddition reactions

A series of trifluoromethanesulfonate (OTf) salts of N-heterocyclic phospheniums (NHP) bearing phenyl (1a), para-methoxyphenyl (1b), 2,6-diisopropylphenyl (1c) and mesityl (1d) substituents is reported. The compounds are made by a modification to a literature procedure that improves the overall yields for and by 15 and 23%, respectively. Two unwanted side-products in the synthesis of , the diammonium salt, [(2,6-iPr-C6H3)N(H)2CH2CH2N(H)2(2,6-iPr-C6H3)]Cl2 (4) and the bisphosphine (2,6-iPr-C6H3)N(PCl2)CH2CH2N(PCl2)(2,6-iPr-C6H3) (5), are crystallographically characterized, as is the intermediate cyclic chlorophosphine, C1PN(4-OMe-C6H4)CH2CH2N(4-OMe-C6H4) (3b). The phenyl-substituted NHP is fully characterized, including by X-ray crystallography, for the first time; this compound contains a short P-O contact of 2.1850(14) A. Cycloaddition reactions of with 2,3-dimethyl-1,3-butadiene give the expected spirocyclic phospholeniums, 7,8-dimethyl-1,4-diaryl-1,4-diaza-5-phopshoniaspiro[4.4]non-7-ene, as their OTf salts (6a-d), while reactions with N,N'-dimesityl-1,4-diaza-1,3-butadiene give, except in the case of , which is too bulky to react, the aza analogues, 1,4-dimesityl-6,9-diaryl-1,4,6,9-tetraaza-5-phosphoniaspiro[4.4]non-2-ene (7a, 7b and 7d). The sterically congested is in thermal equilibrium with and free diazadiene, and undergoes a substitution reaction with 2,3-dimethyl-1,3-butadiene to give .     

256. Steroids and sex hormones. 247. The partial synthesis of tetrahydrostapelogenin

A partial synthesis of tetrahydrostapelogenin ( 5 ), a hydrogenation product of stapelogenin ( 4 ), is described, proofing the structure of 4 proposed by Reichstein [2–3].     

Lithium fluoroarylamidinates: syntheses, structures, and reactions

Lithium fluoroarylamidinates [(Ar(F)C(NSiMe(3))(2)Li)(n).xD] (Ar(F) = 4-CF(3)C(6)H(4), n = 2, D = OEt(2), x = 1 (2a); n = 1, D = TMEDA, x = 1 (4a); Ar(F) = 2-FC(6)H(4), n = 2, D = OEt(2), x = 1 (2b); Ar(F) = 4-FC(6)H(4), n = 2, D = OEt(2), x = 2 (2c); Ar(F) = 2,6-F(2)C(6)H(3), n = 2, D = OEt(2), x = 1 (2d); n = 2, D = 2,6-F(2)C(6)H(3)CN, x = 2 (3d); Ar(F) = C(6)F(5), n= 2, D = OEt(2), x = 1 (2e), n = 1, D = TMEDA, x = 1 (4e); n = 1, x = 2, D = OEt(2) (5e); D = THF (6e)) were prepared by the well-known method from LiN(SiMe(3))(2) and the corresponding nitrile in diethyl ether or by addition of the appropriate donor D to the respective diethyl ether complexes. Depending on the substituents at the aryl group and on the donors D, three different types of structures were confirmed by X-ray crystallography. Hydrolysis of 2e gave C(6)F(5)C(NSiMe(3))N(H)SiMe(3) (7e) and C(6)F(5)C(NH)N(H)SiMe(3) (8e). The lithium fluoroarylamidinates 2a-2d react with Me(3)SiCl to give the corresponding tris(trimethylsilyl)fluoroarylamidines Ar(F)C(NSiMe(3))N(SiMe(3))(2) (9a-9d). Attempts to prepare C(6)F(5)C(NSiMe(3))N(SiMe(3))(2) from 2e and Me(3)SiCl failed; however, the unprecedented cage [[C(6)F(5)C(NSiMe(3))(2)Li](4)LiF] (10e) in which a fluoride center is surrounded by a distorted trigonal bipyramid of five Li atoms was obtained from this reaction.     

Palladium-assisted organic reactions: VIII. Simple syntheses of 2,3-disubstituted phthalimidines

Electron-poor alkenes such as alkyl acrylates have been found to insert into the aromatic carbon—palladium bond in orthobromobenzamides under the conditions of the Heck reaction. For primary and secondary benzamides a further palladium-catalysed reaction occurs to yield 3-substituted, or 2,3-disubstituted phthalimidines.