Straightforward Synthesis of α,β-Unsaturated Thioesters via Ruthenium-Catalyzed Olefin Cross-Metathesis with Thioacrylate

The cross-metathesis reaction of S-ethyl thioacrylate with a variety of olefins is effectively catalyzed by using a ruthenium benzylidene olefin metathesis catalyst. This reaction provides a convenient and versatile route to substituted α,β-unsaturated thioesters, key building blocks in organic synthesis.

Formal Synthesis of the Anti-Angiogenic Polyketide (-)-Borrelidin under Asymmetric Catalytic Control

Borrelidin (1) is a polyketide that possesses extremely potent anti-angiogenesis activity. This paper describes its formal total synthesis by the most efficient route to date. This modular approach takes optimal benefit of asymmetric catalysis and permits the synthesis of analogues; in addition, the high yields and selectivities obtained eliminate the need for separation of stereoisomers. The upper half of borrelidin has been accessed by iterative copper-catalysed asymmetric conjugate addition of methylmagnesium bromide, whereas synthesis of the lower half of the molecule was achieved by relying on asymmetric hydrogenation and cross-methathesis as key steps

Synthesis of Optically Active Bifunctional Building Blocks through Enantioselective Copper-Catalyzed Allylic Alkylation Using Grignard Reagents

Enantioselective copper-catalyzed allylic alkylations were performed on allylic bromides with a protected hydroxyl or amine functional group using several Grignard reagents and Taniaphos L1 as a ligand. The terminal olefin moiety in the products was transformed into various functional groups without racemization, providing facile access to a variety of versatile bifunctional chiral building blocks.

Stereoselective Synthesis of (<i>R</i>)-all-<i>trans</i>-13,14-Dihydroretinol and -Retinoic Acid.

Vitamin A (or all-trans-retinol) metabolites are involved in a wide range of cellular processes. However, the investigation of their biological role is hampered due to their very limited availability. Herein we report a stereoselective total synthesis of the vitamin A metabolites (R)-all-trans-13,14-dihydroretinol and -retinoic acid, applying an E-selective HWE olefination and a Ru(II) catalyzed intramolecular 7- endo-dig hydrosilylation as the key steps. </p

Chiral separation by enantioselective liquid–liquid extraction

The literature on enantioselective liquid–liquid extraction (ELLE) spans more than half a century of research. Nonetheless, a comprehensive overview has not appeared during the past few decades. Enantioselective liquid–liquid extraction is a technology of interest for a wide range of chemists and chemical engineers in the fields of fine chemicals, pharmaceuticals, agrochemicals, fragrances and foods. In this review the principles and advances of resolution through enantioselective liquid–liquid extraction are discussed, starting with an introduction on the principles of enantioselective liquid–liquid extraction including host–guest chemistry, extraction and phase transfer mechanisms, and multistage liquid–liquid extraction processing. Then the literature on enantioselective liquid–liquid extraction systems is reviewed, structured on extractant classes. The following extractant classes are considered: crown ether based extractants, metal complexes and metalloids, extractants based on tartrates, and a final section with all other types of chiral extractants.

Racemic Total Synthesis of Elmonin and Pratenone A, from Streptomyces, Using a Common Intermediate Prepared by peri-Directed C-H Functionalization

[Image: see text] The first total synthesis of elmonin and pratenone A, two complex rearranged angucyclinones from Streptomyces, is reported. Using peri-directed C–H functionalization, the key naphthalene fragment present in both synthetic targets was efficiently prepared. Coupling to two anisole-derived fragments gave access to the natural products, in which elmonin was prepared using a biomimetic spiro-ketalization

Synthesis of Solution-Phase Phosphoramidite and Phosphite Ligand Libraries and Their In Situ Screening in the Rhodium-Catalyzed Asymmetric Addition of Arylboronic Acids

Herein, we report the automated parallel synthesis of solution-phase libraries of phosphoramidite ligands for the development of enantioselective catalysts. The ligand libraries are screened in situ in the asymmetric rhodium-catalyzed addition of arylboronic acids to aldehydes and imines. It is shown that the described methodology results in the straightforward discovery of leads for highly efficient enantioselective catalysts.

Enantiomerically pure β-phenylalanine analogues from α–β-phenylalanine mixtures in a single reactive extraction step

An efficient and selective method for the extraction of α-amino acids in preference over their β-isomers using PdCl2(PPh3)2 was discovered, which enables the separation of product mixtures obtained in the enantioselective enzymatic formation of β-amino acids.

Chemical Synthesis of Cell Wall Constituents of Mycobacterium tuberculosis

The pathogen Mycobacterium tuberculosis (Mtb), causing tuberculosis disease, features an extraordinary thick cell envelope, rich in Mtb-specific lipids, glycolipids, and glycans. These cell wall components are often directly involved in host-pathogen interaction and recognition, intracellular survival, and virulence. For decades, these mycobacterial natural products have been of great interest for immunology and synthetic chemistry alike, due to their complex molecular structure and the biological functions arising from it. The synthesis of many of these constituents has been achieved and aided the elucidation of their function by utilizing the synthetic material to study Mtb immunology. This review summarizes the synthetic efforts of a quarter century of total synthesis and highlights how the synthesis layed the foundation for immunological studies as well as drove the field of organic synthesis and catalysis to efficiently access these complex natural products

Site-selective introduction of thiols in unprotected glycosides

Thioglycosides or S-linked-glycosides are important glycomimetics. These thioglycosides are often prepared by glycosylating deoxythio sugar acceptors, which are synthesized via elaborate protecting group manipulations. We discovered that a carbonyl group, formed by site-selective oxidation of unprotected saccharides, can be converted into a thiol moiety. The transformation involves SN1-substitution of a chloro-azo intermediate, formed by oxidation of the corresponding trityl hydrazone, with a thiol. The prepared deoxythio sugars provide, in combination with the recently developed protecting group-free glycosylation of glycosyl fluorides, a protecting group-free synthesis of thioglycosides.</p