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Relevant academic research and scientific papers

Enantioselective copper-catalyzed conjugate additions of in situ generated organozirconium reagents to N-heterocyclic Michael acceptors

Stereoselective conjugate additions of organometallic reagents provide access to many useful chiral compounds. In this work, we have studied the enantioselective Cu-catalyzed conjugate addition of organozirconium reagents, which were generated in situ by

Catalytic enantioselective addition of alkylzirconium reagents to aliphatic aldehydes

A catalytic methodology for the enantioselective addition of alkylzirconium reagents to aliphatic aldehydes is reported here. The versatile and readily accessible chiral Ph-BINMOL ligand, in the presence of Ti(OiPr)4 and a zinc salt, facilitates the reaction, which proceeds under mild conditions and is compatible with functionalized nucleophiles. The alkylzirconium reagents are conveniently generated in situ by hydrozirconation of alkenes with the Schwartz reagent. This work is a continuation of our previous work on aromatic aldehydes.

Mechanistic Studies on a Cu-Catalyzed Asymmetric Allylic Alkylation with Cyclic Racemic Starting Materials

Mechanistic studies on Cu-catalyzed asymmetric additions of alkylzirconocene nucleophiles to racemic allylic halide electrophiles were conducted using a combination of isotopic labeling, NMR spectroscopy, kinetic modeling, structure-activity relationships, and new reaction development. Kinetic and dynamic NMR spectroscopic studies provided insight into the oligomeric Cu-ligand complexes, which evolve during the course of the reaction to become faster and more highly enantioselective. The Cu-counterions play a role in both selecting different pathways and in racemizing the starting material via formation of an allyl iodide intermediate. We quantify the rate of Cu-catalyzed allyl iodide isomerization and identify a series of conditions under which the formation and racemization of the allyl iodide occurs. We developed reaction conditions where racemic allylic phosphates are suitable substrates using new phosphoramidite ligand D. D also allows highly enantioselective addition to racemic seven-membered-ring allyl chlorides for the first time.1H and2H NMR spectroscopy experiments on reactions using allylic phosphates showed the importance of allyl chloride intermediates, which form either by the action of TMSCl or from an adventitious chloride source. Overall these studies support a mechanism where complex oligomeric catalysts both racemize the starting material and select one enantiomer for a highly enantioselective reaction. It is anticipated that this work will enable extension of copper-catalyzed asymmetric reactions and provide understanding on how to develop dynamic kinetic asymmetric transformations more broadly.

Development of Axially Chiral Cyclo-Biaryldiol Ligands with Adjustable Dihedral Angles

A new type of axially chiral cyclo-[1,1′-biphenyl]-2,2′-diol (CYCNOL) ligands with adjustable dihedral angles have been developed by varying the bridge chain length. Eight-, nine- and ten-membered cyclo-ligands were prepared and evaluated by using two representative examples: enantioselective additions of diethylzinc to aldehydes and organometallic reagents to enones. The results revealed that the fine regulation of dihedral angles through variation of the bridge chain length was effective in the asymmetric synthesis.

Non-stabilized nucleophiles in Cu-catalysed dynamic kinetic asymmetric allylic alkylation

The development of new reactions forming asymmetric carbon-carbon bonds has enabled chemists to synthesize a broad range of important carbon-containing molecules, including pharmaceutical agents, fragrances and polymers1. Most strategies to obtain enantiomerically enriched molecules rely on either generating new stereogenic centres fromprochiral substratesor resolving racemicmixtures of enantiomers.Analternative strategy-dynamic kinetic asymmetric transformation-involves the transformation of a racemic starting material into a single enantiomer product, with greater than 50 per centmaximumyield2,3. The use of stabilized nucleophiles (pKaa is the acid dissociation constant) in palladium-catalysed asymmetric allylic alkylation reactions has proved to be extremely versatile in these processes4,5. Conversely, the use of non-stabilized nucleophiles insuch reactions is difficultand remains a key challenge6-9. Herewe report a copper-catalyseddynamic kinetic asymmetric transformation using racemic substrates and alkyl nucleophiles. These nucleophiles have a pKa of ≥ 50, more than 25 orders of magnitude more basic than the nucleophiles that are typically used in such transformations. Organometallic reagents are generatedin situ fromalkenes byhydrometallation and givehighly enantioenriched productsunder mild reaction conditions. The method is used to synthesize natural products that possess activity against tuberculosis and leprosy, and an inhibitor ofpara-aminobenzoate biosynthesis. Mechanistic studies indicate that the reaction proceeds through a rapidly isomerizing intermediate.We anticipate that this approach will be a valuable complement to existing asymmetric catalytic methods.

ASYMMETRIC SYNTHESIS OF ORGANIC COMPOUNDS

The present invention provides processes for the production of chiral compounds in a stereoisomeric excess. The present processes involve reacting a hydrometallated alkene compound with a compound comprising a conjugated-bond system under conditions such

Hydrozirconation of first-generation allyl-functionalized dendrimers and dendrimer model compounds

Several allyl-functionalized dendrimers and mono-functional model compounds have been prepared. These have been hydrozirconated using [Cp2ZrHCl]x to give zirconocene terminated dendrimers. These dendrimers have been characterized usi