regioselectivity obtained by using non-covalent interactionskanai/seminar/pdf/lit_sakai_m1.pdf ·...
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Regioselectivity Obtained by Using Non-covalent Interactions
2017/4/15
M1 Kentaro Sakai
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1. Introduction
2. Regioselective Reaction Using the Ion-pair Interaction
3. Regioselective Reaction Using the Hydrogen Bonding
4. Summary
2/42Today’s Topics
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1. Introduction
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Example of Non-covalent Interactions4/42
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5/42Example of Enantioselective Reaction Using Non-covalent Interaction
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6/42Proposed Catalytic Cycle
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7/42①The Presence of Innate Reactivity
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8/42②The Number of Choices
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9/42Summary of Section 1
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2. Regioselective Catalyst Using the Ion-pair Interaction
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Ion-pair Interaction11/42
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Regioselective Reaction Using Ion-pair Interaction12/42
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Importance of the Presence of Cation Charge 13/42
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Importance of the Presence of Anion Charge 14/42
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Importance of Substrate and Ligand Interaction 15/42
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Assumed Reaction Mechanism16/42
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Substrate Scope 1 (disubstituted)17/42
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Substrate Scope 2 (monosubstituted)18/42
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Application? Limitation?19/42
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A Solution of the Problem20/42
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21/42Summary of Section 2
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3. Regioselective Catalyst Using the Hydrogen Bonding
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Regioselective Reactions Using Hydrogen Bonding23/42
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Regioselective Acylation of Polyol24/42
Catalyst-controled regioselectivity was observed.
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The Side-chain Effect25/42
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Importance of Free NH of Catalyst26/42
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Importance of Free OH of Substrate27/42
6-OH group of the substrate was important for regioselectivity.
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Important Sites for Regioselectivity Expression28/42
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Solvent Effect 29/42
Polar solvent decreased yields and regioselectivity.
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No Effect of Additives30/42
The presence of alcohol didn’t inhibit the selective acylation.
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Proposed Reaction Mechanism31/42
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Various Acyl Donor32/42
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Acylation of Other Structures33/42
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Chemoselective Acylation of 1,n-diol (1)34/42
It was difficult to suppress the double acylation in the previous method.
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Chemoselective Acylation of 1,n-diol (2)35/42
Acylation with catalyst A avoided double functionalization.
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Solvent Effect on Chemoselectivity36/42
Hydrogen bonds may be involved in this reaction.
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The Effect of Chain Length37/42
Long chain decreased selectivity.
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Proposed Mechanism of the Phenomenon38/42
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My Idea: Regioselective Acylation of 1,n-diol ?39/42
May such regioselective reaction be possible?
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40/42Summary of Section 3
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4. Summary
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42/42Summary of Today’s Literature Seminar