Year 3 CH3E4 notes: Asymmetric Catalysis, Prof Martin Wills You are aware of t

Year 3 CH3E4 notes: Asymmetric Catalysis, Prof Martin Wills You are aware of t www.phwiki.com

Year 3 CH3E4 notes: Asymmetric Catalysis, Prof Martin Wills You are aware of t

Hicks, Cortney, Morning Host has reference to this Academic Journal, PHwiki organized this Journal Year 3 CH3E4 notes: Asymmetric Catalysis, Prof Martin Wills You are aware of the importance of chirality. This section will focus on asymmetric catalysis, i.e. the use of a catalyst to create new enantiomerically pure molecules. This can be achieved in several ways: M Wills CH3E4 notes 1) A metal may template the reaction, e.g. Sharpless epoxidation of allylic alcohols: 2) A covalent intermediate may be as long as med: M Wills CH3E4 notes 3) The reaction may take place within an asymmetric environment controlled by an external source: The key features of these approaches will be described in addition to examples from the literature will be described. Some examples of enantiomerically pure drugs: M Wills CH3E4 notes Oxidation reactions of alkenes. Historical: The Sharpless epoxidation was one of the first examples of asymmetric catalysis (see earlier slide). The Sharpless dihydroxylation reaction employs lig in addition to -acceleration to turn the known dihydroxyation reaction into an asymmetric version.

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M Wills CH3E4 notes Oxidation reactions of alkenes. Most recent evidence favours the [3+2] addition mechanism: K. B. Sharpless et al, J. Am. Chem. Soc. 1997, 119, 9907. M Wills CH3E4 notes Oxidation reactions of alkenes. Jacobsen epoxidation of alkenes: The iodine reagent transfers its oxygen atom to Mn, then the Mn tranfers in to the alkene in a second step. The chirality of the catalyst controls the absolute configuration. Advantage You are not limited to allylic alcohols Sharpless aminodihydroxylation is a closely-related process M Wills CH3E4 notes Reduction reactions of Double bonds (C=C, C=N, C=O).

M Wills CH3E4 notes Reduction reactions of C=C Double bonds using Rh(I) complexes– representative examples. M Wills CH3E4 notes Reduction reactions of Double bonds using catalysts derived from Ru(II) (C=C). M Wills CH3E4 notes Reduction reactions of isolated C=C double bonds can be achieved with variants of Crabtree’s catalyst.

M Wills CH3E4 notes Reduction reactions of C=O Double bonds using organometallic complexes. M Wills CH3E4 notes Reduction reactions of C=O Double bonds using organometallic complexes. Dynamic kinetic resolution can result in as long as mation of two chiral centres: Ketone reduction by pressure hydrogenation (i.e. hydrogen gas) can be achieved using a modified catalyst containing a diamine, which changes the mechanism. M Wills CH3E4 notes

M Wills CH3E4 notes The use of hydride type reagents. More contemporary focus is on asymmetric transfer hydrogenation in addition to on organocatalysis. Oxazaborolidines require a relatively high catalyst loading of 10%, But are effective in several applications. Transfer hydrogenation – Ru catalysts. M Wills CH3E4 notes Examples of reductions using transfer hydrogenation with metal complexes: add C=O in addition to C=N reductions. M Wills CH3E4 notes

M Wills CH3E4 notes Asymmetric transfer hydrogenation by organocatalysis. M Wills CH3E4 notes Formation of chiral centres by nucleophilic additions to unsaturated bonds. Diethylzinc additions Another interesting fact: DAIB of 15% ee will give a product of 95% ee! This is because the dimer made from one of each enantiomer is more stable, in addition to does not split up to enter the catalytic cycle. Ph Ph Ph H H H More applications of organocatalysis. M Wills CH3E4 notes

M Wills CH3E4 notes More applications of organocatalysis which proceed via as long as mation of an enamine – bonds to C atoms. C=C reduction by organocatalysis. 20 M Wills CH3E4 notes Additions to C=O – aldol reactions are a very important class of synthetic reaction.

Other examples of metal/lig in addition to -catalysed asymmetric aldol reactions. M Wills CH3E4 notes Cycloaddition reactions can be catalysed by Lewis acid/chiral lig in addition to s. The lig in addition to in addition to metal choice can have a dramatic effect: There are many other similar catalysts as long as Lewis-acid catalysed Diels-Alder reactions. Organocatalysts can be applied to Diels-Alder reactions, by as long as ming a cationic intermediate: 24

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M Wills CH3E4 notes Allylic substitution reactions are powerful methods as long as as long as ming C-C bonds. M Wills CH3E4 notes Allylic substitution reactions – examples of lig in addition to s in addition to reactions. Allylic substitution reactions – examples of lig in addition to s in addition to reactions.

M Wills CH3E4 notes Uses of enzymes in asymmetric synthesis. this can Invert an alcohol overall. M Wills CH3E4 notes Enzyme catalysis: amine oxidation. Chem. Commun. 2010, 7918-7920. Uses of dehydrogenase enzymes in synthesis. For a nice example of use of an enzyme in dynamic kinetic resolution to make side chain of taxol see: D. B. Berkowitz et al. Chem. Commun. 2011, 2420-2422. M Wills CH3E4 notes Review on directed evolution by Reetz: M. T. Reetz, Angew. Chem. Int. Ed. 2011, 50, 138-174. By undertaking cycles of directed evolution, highly selective enzymes can be prepared, as shown by the example of desymmetrisation (Baeyer-Villiger reaction) shown below:

M Wills CH3E4 notes Other asymmetric reactions – as long as interest. Asymmetric catalysis – Isomerisation. M Wills CH3E4 notes There are many other reactions which have been converted into asymmetric processes. Other reactions: Hydrosilylation Hydroacylation Hydrocyanation Epoxidation using iminium salts Asymmetric allylation Hetero Diels-Alders 1,3-dipolar cycloadditions. [2+2] cycloadditions Cyclopropanation Cross coupling reactions Conjugate addition reactions Etc. etc.

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