A flexible common approach for the asymmetric syntheses of sphingofungins E and F is reported, with efficient use of both diastereomers of the Baylis–Hillman adduct in a stereoconvergent manner. Pronounced steric effects of the 2-substituents in diastereoselective dihydroxylations of (E)-2-hydroxymethyl-2,3-alkenoates were observed. This strategy also allowed full control over the absolute configurations of the quaternary stereocenters in α-substituted amino acids through tunable site-specific adjustment of oxidation states.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

A weak base, CsOAc, promotes Suzuki–Miyaura cross-coupling and related Pd-catalyzed reactions under anhydrous conditions as effectively as stronger bases. Aryl triflates exhibit unusual reaction rates, which are comparable to that of bromoarenes. A neglected six-membered transition-state model was proposed to give alternative insight into the key process of transmetalation.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Both cis- and trans-3-hydroxy-L-pipecolic acids are synthesized from a common chiral intermediate 7 by a short and flexible route. The stereospecific inversion of C-3 was achieved by the formation of an oxazoline followed by acidic ring cleavage. The overall yields are 27 % and 30 %, respectively, in 12 and 10 linear steps. Several versatile chiral building blocks are also accessible by this diastereodivergent synthesis. Unlike the chiral pool approach, our synthetic strategy is not limited by the availability of starting materials.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)