BOSS 12 conference report Siti Aishah Hasbullah

CONFERENCE REPORTBOSS 12

Siti Aishah Hasbullah

20th October 2010

Prof. Eric JACOBSEN(HARVARD UNIVERSITY, Cambridge, United

States)

Prof. David MACMILLAN(PRINCETON UNIVERSITY, Princeton, United

States)

Tetrahedron Lecture

Prof. David MacMillan

Princeton University

Tetrahedron Lecture 1: The Advent and Growth of Organocatalysis and Iminium Catalysis

The Roots of Organocatalysis: 19th Century Reaction Discovery

H

OHCN

O

OHWohler, F.; Liebig, J. Annal. Pharm. 1832, 3,249

H CN

HO CN OH

Basic for carbene catalysis

O

Me

O

Me

HO

O

OHO

3 mol% cat

DMFNH

CO2H

Cat. (S)-proline

The Early Use of Organic Catalysis in Enantioselective Synthesis: Hajos-Parrish

-Intramolecular Aldol: Hajos-Parrish, JOC, 1974,39,1615

-Extraordinary result that was well received by the chemical synthesis community

- Betweeen 1960 – 2001, no review articles on the collective use of organocatalyst.

Enantioselective Catalysis using Small Organic Molecules: Epoxidation

O10 mol% cat

Oxone

50 - 98% ee

O

OO

O

O

O

OO

OO

O

N

OF

Yang CatalystJACS, 1996, 118, 491

Shi catalystJACS, 1996, 118,9806

Denmark CatalystJOC,1998, 63, 2810

-Employed ketones as enantioselectives catalysts

-Demonstrated that organic catalyst could be employed to solve major chemical problems

-Involved the invention of a single catalyst for a single reaction type

MacMillan: The Advent of Iminium Catalysis and the Field of Organocatalysis

New Strategies for Organic Catalysis: The First Highly Enantioselective Organocatalytic Diels-Alder

Reaction

MacMillan: The Advent of Iminium Catalysis and the Field of

Organocatalysis..Cont…..

This manuscript conceptualized the field of organocatalysis for the first time in 3 important ways:

1. Outlined the potential benefits of using organic molecules as asymmetric catalysts for industry or academia based on cost, availability and ease to use

2. Introduced the concept of generic mode of activation for organic catalysis that could be used over many reaction types

3. Introduced for the first time, the terminology organocatalysis, organic catalysis and organocatalytic

Tetrahedron Lecture 2: Enamine Catalysis: Teaching and Old Dog Some Tricks

Enamine Catalysis : Early Adoption in Catalysis

- Woodward-Wieland-Miescher enamine cyclization for steroid synthesis

O

Me H

MeOH

OHH5IO6

O

Me H

MeO

O

O

Me H

Me

NH

HOAcbenzene

CHO

JACS, 1952, 74, 4223

OH

OO

O

HH

Me

OONH

NaOH

O

O

Me

OH

HOOH

O

O

O

O

Me

Helv. Chim. Acta, 1950, 33, 2215

Bifunctional Enamine Catalysis: Generic Induction Platform

Use of proline or proline-type activation a widely exploited mode of ketone activation

R1

R

O

NH O

OH

X=Y

X Y HN

O

H

R

R'O

N NR

R

Amination

PhNO2

Nitro olefinaddition

H Me

MeO

Cross-Aldol

Org. Lett. 2001, 2423

Org. Lett. 2001, 573

Unconventional Reactivity Profiles Induced by Chiral Primary Amines Catalysis

Paolo Melchiorre,

Inst. Chem Research of Catalonia

Recent Advances in Stereoselectives Synthesis

Ilan Marek

Technion-Israel Institute of Technology

Directed Evolution of Enzymes: New Biocatalysts for Organic Synthesis

Nicholas J. Turner,

University of Manchester

Enantioselective Biocatalytic Oxidative Desymmetrization of Substituted Pyrrolidines

Seeking Fundamental Insights and Practical Reaction: Asymmetric Catalysis as a Synthetic and Mechanistic Tool

Eric Jacobsen,

Harvard University

Enantioselective Thiourea-Catalyzed Cationic Polycyclizations

Ruthenium Catalyzed Directing Group-Free C2-Selective Carbenoid Functionalization of Indoles by α-Aryldiazoesters

Org. Lett, 2010, 12, 604

Ruthenium Diversity: Alkynes, Carbenes and C-H Bonds

Pierre H. Dixneuf,

Rennes, Frances

Sequential Synthesis of Furans from Alkynes

National University of Malaysia

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