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Synthetically important β-hydroxyacylsilanes are available with good to excellent diastereoselectivity under mild conditions.

A facile total synthesis of nonsymmetrical 14-membered macrocyclic bis-lactone, 4-ketoclonostachydiol has been demonstrated in a convergent approach. The synthetic strategy has been unambiguously successful towards incorporating all the three stereogenic centers present in the molecule with an overall yield of 0.9%. The key synthetic step includes MacMillan hydroxylation and Grubbs ring-closing metathesis reactions to furnish the core skeleton.

A stereoselective synthesis of the C1–C11 fragment of zincophorin was achieved by using an intramolecular oxetane ring opening reaction as the key step. The oxetane moiety was synthesized by employing a desymmetrization protocol developed at our group and a non-Evans syn aldol as the key steps toward the synthesis.

A convergent enantioselective synthesis of panclicin-D has been reported from simple octanal using syn aldol reaction via intramolecular S N 2 displacement reaction for the first time towards the construction of anti-β-lactones in panclicin-D. The key steps involved are C-allylation, asymmetric aldolization under Crimmins condition, intramolecular S N 2 displacement, and Mitsunobu esterification reaction.

Three complementary strategies have been explored to obtain stereodefined 1,3 diols starting from easily accessible syn β-hydroxy acylsilanes: fluoride induced migrations of substituents on silicon, a Grignard addition followed by protodesilylation and Tischenko-type reactions. Preliminary data on scope and limitations of these processes are presented.

The first total synthesis of pinolide, a nonsymmetrical ten-membered macrocyclic, is described starting from readily available (–)-tartaric and L-ascorbic acid. The key synthetic steps include Barbier allylation, Yamaguchi esterification and ring-closing metathesis (RCM) reactions. The synthetic strategy has been successful for the construction of the ten-membered core skeleton. A facile and convergent approach enabled the incorporation of all the four stereogenic centers present in the molecule.

Trans-2,6-substituted 2-allylated pyrans are stereoselectively prepared by iodine catalyzed allylation of the corresponding tetrahydro-2H-pyranols.

The redox isomerization processes and tandem isomerization–aldolization reactions, mediated by nickel catalysts, offer new versatile entries to acylsilanes. For the second reaction, high diastereoselectivities, up to 98:2, have been obtained with bulky substituents on silicon.

A small library of 26 arylhetaryl systems containing fluorinated side chains, e.g. (III) and (V), is prepared by means of Suzuki—Miyaura and Still cross coupling reactions.