Synthesis of β-Glucuronides of Estradiol,Ethynylestradiol and Estrone

ABSTRACT

Improved syntheses for the 3-β-D-glucuronides of the steroidal sex hormones 17β-estradiol, 17α-ethynylestradiol and estrone are reported employing boron trifluoride diethyl etherate catalysis with tetraacetylated glucuronic acid or the corresponding imidate.     

Chiral linker 5: scope and limitations of arylsubstituted m-hydrobenzoins as solid supported open chain chiral auxiliaries for diastereoselective syntheses

The applicability of five aryl substituted m-hydrobenzoin ethers already tested in the L-Selectride^® mediated stereoselective reduction of phenylglyoxylates as open chain chiral auxiliaries was further investigated via the α-alkylation of propionates, the addition of n-BuZnCl to phenylglyoxylates and the Diels–Alder reaction of acrylates with cyclopentadiene as model reactions. As up to 90% de could be achieved in the solution phase, two optimized auxiliary structures were immobilized on commercially available Wang-resin and applied as a reusable solid supported chiral auxiliaries in the same type of reactions.     

Even and odd diagonals in doubly stochastic matrices

The existence of even or odd diagonals in doubly stochastic matrices depends on the number of positive elements in the matrix. The optimal general lower bound in order to guarantee the existence of such diagonals is determined, as well as their minimal number for given number of positive elements. The results are related to the characterization of even doubly stochastic matrices in connection with Birkhoff's algorithm.