Maurice Santelli

(2001). CHEMICAL AND BIOCHEMICAL HYDROXYLATIONS OF STEROIDS. A REVIEW. Organic Preparations and Procedures International: Vol. 33, No. 1, pp. 1-58.

The cis,cis,cis-1,2,3,4-Tetrakis(diphenylphosphinomethyl)cyclopentane –[PdCl(C₃H₅)]₂ system catalyses the cross coupling of aryl bromides with arylboronic acids with very high substrate–catalyst ratios in good yields; a turnover number of 28000000 can be obtained for the addition of 4-bromobenzophenone to benzeneboronic acid in the presence of this catalyst.

[Bis(diphenylphosphino)alkane]bis(propenyl)ruthenium(II) and [bis(diphenylphosphino)ethane]palladium(II) complexes catalyse the aldol addition of 1-methoxy-2-methyl-1-trimethylsilyloxy-propene to aldehydes and ketones under neutral conditions affording the corresponding 3-hydroxymethylesters in good yields. A ratio substrate/catalyst of 1000 can be employed with the palladium system without loss of efficiency.

An efficient synthesis of 11-thia steroids was achieved via an intramolecular Diels-Alder cycloaddition of orthoquinodimethane as the key step. The major isomer was transformed into sulfoxide 7. The vinyl group of the steroid 7 has been oxidized using the Wacker process to the corresponding ketone 8 in good yield.

The cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)-cyclopentan e/[PdCl(C₃H₅)]₂ system catalyses allylic amination in good yields with a very high substrate/catalyst ratio; a turnover number of 680 000 and a turnover frequency of 8125 h⁻¹ can be obtained for the addition of dipropylamine to allyl acetate in the presence of this catalyst.