•Expedient assembly of the conidiogenone core via nitrile-assisted TMM diyl cycloaddition•Regio- and diastereoselective decorations D-ring scaffold•Divergent synthesis six (?)-conidiogenones•First total (?)-conidiogenones E, F, 12?-hydroxyconidiogenone C Herein, we constructed fused tetracyclic natural products by single-step tandem cyclizations diazo, allene, olefin moieties in linear precurso...

Esters of crotonic acid were brominated on a multigramme scale using a free radical procedure. A phase transfer catalysed fluorination transformed these species to the 4-fluorobut-2E-enoates reproducibly and at scale (48–53%, ca. 300 mmol). Asymmetric dihydroxylation reactions were then used to transform the butenoate, ultimately into all four diastereoisomers of a versatile fluorinated C4 buil...

Post-translational modifications play an important role in regulating protein structure and function in health and disease. Ubiquitylation is one example for such a modification wherein both the extent (polyversus mono-ubiquitylation) and the sequence position of this modification dictates the function and fate of the ubiquitylated protein. In the ubiquitylation process, three distinct enzymes,...

An ene-yne cross metathesis of silyl substituted alkynes and alkenes followed by a Diels-Alder reaction of the metathesis product 2-silyl-1,3-dienes has been developed. The dienes thus prepared in situ were shown to participate in highly diastereoselective Diels-Alder reactions. In one case the silicon substituted Diels-Alder cycloadduct was subsequently used without isolation and purification ...

The development of new reactions is important to improve the toolbox organic chemistry. One way nudge a reaction undergo pathway different from what it normally takes. Stereoinvertive SN2 known be intolerant bulky tertiary carbon centers, which tend proceed through SN1 pathways form racemized products. This leads long-standing challenge in synthesis; that is, how prepare enantiopure compounds s...

Derivatives of 3 -amino-5-cholestene (3 -cholesterylamine) are of substantial interest as cellular probes and have potential medicinal applications. However, existing syntheses of 3 -amino-5-cholestene are of limited preparative utility. We report here a practical method for the stereoselective preparation of 3 -amino-5-cholestene, 3 -chloro-5-cholestene, 3 -bromo-5-cholestene, and 3 -iodo-5-ch...

•Efficient three-component assembly of sulfondiimidamides; new analogs sulfonamides•Use unsymmetrical sulfurdiimide reagents is key to success the synthesis•Broad variation at all three nitrogen atoms and carbon substituent•Preparation enantiomerically enriched, chiral sulfur, examples A functional group an arrangement that defines topology reactivity a molecule. The ability modify these two pa...

•Unique axial-to-axial chirality transfer for C–N axial construction•Ability to assemble two vicinal and remote stereogenic axes•Step-economic scalable synthesis of enantioenriched phenanthridinones•Broad scope, good yields, excellent enantioselectivities Axial widely exists in bioactive natural products, pharmaceuticals, chiral materials, ligands catalysts asymmetric catalysis. As such, the ef...

The synthesis and thermal properties of new shape-persistent macrocycles of different sizes decorated with intraannular alkyl chains are described. The alkyl chain length is in all cases sufficient to cross the rings and to fill their interior completely. The investigation of the thermal behavior has shown that the smaller cycles do not exhibit thermotropic mesophases. Single crystal x-ray anal...