Young Chemist s Panel - Review Meeting 2012
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1 Asymmetric Nucleophilic Catalysis Young Chemist s Panel - Review Meeting th th November 2012 Dr. Dave Carbery, Department of Chemistry, University of Bath
2 Setting the Context Catalysing Acyl Transfer with Pyridines The term nucleophilic catalysis is arguably most associated with pyridines. More specifically, 4-dimethylaminopyridine (DMAP) is the catalyst most associated with nucleophilic catalysis. Pyridine demonstrated to promote acetylation of alcohols and phenols by Einhorn and Hollandt (Munich, 1898). In 1967, Litvinenko and Kirichenko (USSR) systematically study the benzoylation of anilines catalysed by structurally diverse pyridines. The presence of DMAP leads to a rate enhancement of x150,000 against the analogous use of Et 3 N, and x6000 compared to pyridine. In 1969, Steglich and Höfle (Munich) independently demonstrate the catalytic activity of DMAP and soon after, 4-pyrrolidinopyridine.
3 Lewis Base Catalysis The chemistry that grew from the original acylation synthetic methodology work concerned pyridine acting as a nucleophilic additive. However, the nucleophilic catalyst functions by forming an acylating species, which has enhanced electrophilicity. In more general terms, DMAP acts as a Lewis basic catalyst, reacting with electrophiles. (Denmark discusses in some detail: Angew. Chem. Int. Ed. 2008, 47, 1560.) More generally, Jansen has discussed 9 possible Lewis acid/base combinations based on the nature of the electron pair donator and acceptor: Donor Acceptor n* σ* π* n n n* n σ* n π σ σ n* σ σ σ π π π n* π σ* π π
4 Strategies for Stereoselective Synthesis via Acyl Transfer Contextualise common stereocontrol strategies used in asymmetric nucleophilic catalysis by alcohol acylation.
5 Strategies for Stereoselective Synthesis via Acyl Transfer Contextualise common stereocontrol strategies used in asymmetric nucleophilic catalysis by alcohol acylation.
6 DMAP-Catalysed Acyl Transfer Consider the DMAP-catalysed reaction of an acid anhydride and an alcohol. Equilibrium formation of a highly electrophilic N-acylpyridinium salt. Donation of electron density from substituent is crucial (no catalysis with pyridine C-2 substituents). Reaction of nucleophile at N-acyl pyridinium, carboxylate acts as base.
7 Chiral Aminopyridines Structure/Activity
8 Chiral Aminopyridines Structural Challenges The powerful catalysts DMAP and PPY are highly symmetrical with two planes of symmetry. Reactive site is pyridine nitrogen (N-1) No catalytic activity if substituted at C-2 How does one effectively desymmetrize a distant lone pair?
9 Chiral Aminopyridines Vedejs Reagent
10 Chiral Aminopyridines Fuji Catalyst
11 Chiral Aminopyridines Yamada Catalyst
12 Chiral Aminopyridines Yamada Catalyst
13 Chiral Aminopyridines Connon Catalyst
14 Chiral Aminopyridines Jeong s Kemp Triacid
15 Chiral Aminopyridines Spivey Atropisomeric Catalyst
16 Chiral Aminopyridines Spivey Atropisomeric Catalyst Synthesis
17 Chiral Aminopyridines Fu Planar Chiral Catalyst
18 Chiral Aminopyridines Fu Planar Chiral Catalyst Resolution Examples
19 Chiral Aminopyridines Fu Planar Chiral Catalyst Resolution Examples
20 Chiral Aminopyridines Fu Planar Chiral Catalyst Resolution Examples
21 Chiral Aminopyridines Fu Planar Chiral Catalyst Fu DKR
22 Chiral Aminopyridines Carbery Helical Catalyst
23 Chiral Aminopyridines Carbery Helical Catalyst
24 Chiral Aminopyridines Carbery Helical Catalyst
25 Chiral Aminopyridines Carbery Helical Catalyst 2 nd Generation Catalyst is Scalable, Selective, Resolution-Free
26 Chiral Aminopyridines Seidel H-Bonding System
27 Chiral Aminopyridines Seidel Anion Binding Model
28 Chiral Imidazoles Miller s Oligopeptides Alcohol Resolution
29 Chiral Imidazoles Miller s Oligopeptides Thioamide Resolution
30 Chiral Imidazoles Histidinyl Systems
31 Chiral Amidines Birman Catalysts
32 Chiral Amidines Birman Catalysts
33 Chiral Amidines Birman Catalysts
34 Chiral Amidines Amidine Catalysts Structure Variation
35 Chiral Amidines Deng/Fossey Amidine
36 Chiral Vicinal Diamines Oriyama Catalysts
37 Chiral Vicinal Diamines Connon Thiol Resolution
38 Chiral Phosphines Vedejs Catalysts
39 Chiral N-heterocyclic Carbenes
40 Asymmetric Nucleophilic Catalysis Outlook and Challenges Alcohols Thorough body of work, but, scope for 3 and saturated substrates (alkyl/alkyl 2 ). Amines Remains a huge challenge. Competitive nucleophilicity. Other elements (P?) Catalysts Commercial availability. Multi-functionality/co-operativity. Modelling and understanding. Reactions C-C bond formations. Almost all are derived from early DMAP chemistry...creativity. Electrophiles E-X... E = sulfonyl, phosphoryl, silyl etc
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