Improved Immobilization of Chiral Bisoxazolines on Silica: Application to Circulating Flow-Type Pack Bed Reactor Su Seong Lee, Jaehong Lim, Jackie Y. Ying.

Slides:

Advertisements

Similar presentations

Outline Introduction Design of catalytic membrane reactor Results

Advertisements

Asymmetric ketone and imine reductions using ruthenium catalysts Jonathan Hopewell, José E. D. Martins and Martin Wills* 1) M. Wills, D. S. Matharu and.

中国科学院大连化学物理研究所万伯顺新型手性 SAA 配体的设计合成与应用研究第五届全国有机化学学术讨论会报告，郑州大学.

30 th ISTC Japan Workshop on Advanced Catalysis Technologies in Russia Fluidized bed catalytic pyrolysis and gasification of biomass for production of.

Humic Science & Technology VIII March 16-18, 2005 Northeastern University Boston, MA, USA martina klučáková pavla žbánková miloslav pekař Brno University.

Jacobsen Catalyst C344. Overview Asymmetric catalysis Lab overview Organometallic reactions Chiral GC analysis Optical Activity.

1 D. A. Evans’ Asymmetric Synthesis — From 80’s Chiral Auxiliary to 90’s Copper Complexes and Their Applications in Total Synthesis Supervisor: Professor.

Pedro J. Pérez Universidad de Huelva Toward Sustainable Chemistry: METhodologies for HEterogenising HOmogenous CATalysts (METHEHOCAT)

Center for Catalysis Research and Innovation

Catalytic Cross-coupling Reactions with Unactivated Alkyl Electrophiles and Alkyl Nucleophiles Heng Su 04/11/2008 Department of Chemistry Brandeis University.

Reporter: Yu Ting Huang Advising Prof: Ru Jong Jeng 1.

Low valent of Vanadium catalyst in organic synthesis.

1 CH402 Asymmetric catalytic reactions Prof M. Wills Think about chiral centres. How would you make these products? Think about how you would make them.

Year 3 CH3E4 notes: Asymmetric Catalysis, Prof Martin Wills

Alkylation by Asymmetric Phase- Transfer Catalysis 张文全.

The application of alkaline metal(Ca, Sr, Ba) complex as catalyst in organic chemistry 张文全 1.

SEPARATION BY ENZYMATICALLY CATALYZED REACTIONS Chapter 10.

Introduction Asymmetric reduction of C=N bonds represents a powerful method for the asymmetric formation of chiral amines. 1 Whilst many methods exist.

Transition-Metal-Catalyzed Enantioselective Insertion of carbenes or carbenoids into the Heteroatom-Hydrogen Bond Reactions Xiaolei Lian

1 Single electron transfer reaction involving 1,3-dicarbonyl compounds and its synthetic applications Reporter: Jie Yu Oct. 31, 2009.

何玉萍 Palladium(II)-Catalyzed Alkene Functionalization.

Career-in-review Keiji Maruoka Reporter: Li Chen Supervisor: Prof. David Zhigang Wang

® HPLC Columns Inertsil ODS-4 is a C18 column developed focusing on superb inertness to basic, acidic, neutral and chelating compounds, which can virtually.

Alexander Stadler and C. Oliver Kappe* 7 th Annual High-Throughput Organic Synthesis Meeting, February 13-15, 2002, San Diego, California Institute of.

Poster 1, Master Thesis, 2000 Beijing University of Chemical Technology, Beijing, China Catalyst global performance Design of the Cu-based Catalyst Pellets.

Dr. Kristoffer Rem Labing-isa

Recoverable and recyclable catalysts for sustainable chemical processes Anna Chrobok Silesian University of Technology, Poland.

In-situ fabrication of functionally graded Al/Mg 2 Si by electromagnetic separation Li Jianguo School of Materials Science and Engineering,

Carbon-Carbon Bond Forming Reactions I. Substitution Reaction II. Addition Reaction.

1 CATALYTIC ASYMMETRIC NOZAKI- HIYAMA-KISHI REACTION: ROLE OF ORGANOCHROMIUM COMPOUNDS AND NOVEL SALEN LIGANDS A RKAJYOTI C HAKRABARTY Prof. Uday Maitra’s.

1 Synthesis and Characterization of N-Heterocyclic Carbene Palladium(II) Complexes. The Catalytic Application on Strecker Synthesis of α- aminonitriles.

Catalytic Enantioselective Allylic Amination of Unactivated Terminal Olefins Via an Ene Reaction / [2,3]-Rearrangement Hongli Bao & Uttam K. Tambar Guillaume.

1 Molecular and Gold Nanoparticles Supported N-Heterocyclic Carbene Silver(I) Complexes – Synthesis, Characterization and Catalytic Applications 學生 : 王趙增.

1 Year 3 CH3E4 notes: Asymmetric Catalysis, Prof Martin Wills Reorganised to highlight key areas to learn and understand. You are aware of the importance.

1 Year 3 CH3E4 notes: Asymmetric Catalysis, Prof Martin Wills You are aware of the importance of chirality. This course will focus on asymmetric.

Recycle packed column reactor: - allow the reactor to operate at high fluid velocities. - a substrate that cannot be completely processed on a single.

Ye Zhu 09/02/10 Burgess’s Group Meeting Chiral Ligands On A Spiro Scaffold for Transition-Metal- Catalyzed Asymmetric Reactions Work by Prof. Zhou Qi-Lin.

Organic Pedagogical Electronic Network Attachment of Molecular Catalysts on Solid Supports - Rh Complex on a Silica Support Jones Group, Georgia Tech Davies.

Supervisor: Yong Huang Reporter: Qian Wang Date: Magical Chiral Spirobiindane Skeletons.

Atom-Economical and Sustainable C-N Bond Formation Reactions from Alcohols and N-Sources via Catalytic Hydrogen Transfer Reactions September 15th, 2015.

金属催化的氧化反应 CYP 450TauD Acc. Chem. Res. 2007, 40, 522–531.

Catalytic Synthesis of α,β- Unsaturated Carbonyl Derivatives 陈殿峰

Homogeneous Catalysis HMC Dr. K.R.Krishnamurthy National Centre for Catalysis Research Indian Institute of Technology,Madras Chennai

Synthesis, structural characterisation and catalytic testing of bioinspired electron transfer catalysts István Pálinkó Department of Organic Chemistry,

Nanocatalysis for Green Synthesis Seminar Research for B.Sc Students.

Enantioselective Reactions Catalyzed by Iron Complexes Pablo Pérez.

Siliceous Mesocellular Foam (MCF) for Green Chemistry

Microchannel Fischer-Tropsch for Biomass-to-Liquids Green Chemistry Conference June 25, 2008 Jeff S. McDaniel.

UNIVERSITA’ DEGLI STUDI DI MILANO PhD IN CHEMICAL SCIENCES XXII CYCLE Daniele Sergio ZERLA Matr. R07227 Tutor: Chiar.mo Prof. E.CESAROTTI Natural and unnatural.

Polymer Supported Reagents & Catalysts

Catalytic Enantioselective Fluorination

Process Intensification Using Particles Across Length Scales Professor Yulong Ding Institute.

The Ph.D. Students’ Day Steve Dierick István E. Markó

Boreskov Institute of Catalysis,

(1 mmol), aniline (1 mmol) or indole (1 mmol) and kojic acid (1 mmol)

PTC Synthesis of the Isoflavanoid S-Equol

(Advisor : Prof. Eric N. Jacobsen)

ALDOL CONDENSATION OF FURFURAL AND CYCLOHEXANONE

Horizon Chromatography

Asymmetric Synthesis Introduction.

Ananda S. Amarasekara. , Onome S

Jidon Janaun1, Naoko Ellis2,

Catalyst Catalysis.

Building Enantioselective Ligands: New Frontiers with Oxazolines

Reporter: Sun Beiqi Supervisor: Prof. Mo Date: 4/8/2016.

Abigail G. Doyle, Department of Chemistry, Princeton University

B-Hydroxysalicylhydrazones: Chiral, non-racemic tridentate catalysts for asymmetric synthesis Shawn R. Hitchcock, Department of Chemistry, Illinois State.

Shawn R. Hitchcock, Department of Chemistry, Illinois State University

1. Palladium Catalyzed Organic Transformations

Diels-Alder in Aqueous Molecular Hosts:

Presentation transcript:

Improved Immobilization of Chiral Bisoxazolines on Silica: Application to Circulating Flow-Type Pack Bed Reactor Su Seong Lee, Jaehong Lim, Jackie Y. Ying Institute of Bioengineering and Nanotechnology Singapore The 12th Annual Green Chemistry and Engineering Conference (June 24-26, 2008) Washington, DC

Chiral Bisoxazoline Ligands Privileged chiral catalyst Yoon, T. P. & Jacobsen, E. N. Science 299,1691, 2003 R1 R2 R1 R2 R3 R2 R2 Cyclopropanation Ene-Reactions Diels-Alder Reactions Allylic substitution Aziridination reactions Mukaiyama Aldol Reactions Enantioselective Henry reaction Enantioselective conjugate addition of carbamates (synthesis of β-amino acids)

Causes of the low enantioselectivities? Silica-Supported Chiral Bisoxazoline Cyclopropanation of styrene < 30% ee Causes of the low enantioselectivities? < 65% ee J. Org. Chem., 66 (26), 8893, 2001 Silica < 55% ee Grafting on MCM Chem. Commun. 1936, 2001

Spherical MCF Microparticles as a Silica Support Spherical, micron-sized MCF particles Packed beds for catalysis and separations Conventional MCF Conventional MCF Advantages Large pore size more than 20 nm  No diffusion problem Easy control of the pore size Excellent mechanical strength Easy isolation of catalysts  Higher activity Easy control of catalyst microenvironment MCF = mesocellular siliceous foam Conventional MCF More efficient packed bed reactor Spherical MCF

Asymmetric cyclopropanation of styrene Interaction of Bisoxazoline with Silica Surface MCF or TMS-capped MCF MCF + AzatBBOX:Cu(II) A C PhNHNH2 Stirring, CH2Cl2 TMS-MCF + AzatBBOX:Cu(II) B D Asymmetric cyclopropanation of styrene + N2CH2CO2Et A B Catalyst Run Yield (%) Trans:Cis Trans (ee%) Cis (ee%) C 1 73 64:36 78 66 2 67 66:34 82 72 D 74:26 91 87 71:29 86 81 After two runs Adv. Synth. Catal. 350, 1295, 2008

Asymmetric cyclopropanation of styrene Influence of Postcapping M C F M C F (HMDS) Asymmetric cyclopropanation of styrene % ee (for trans isomer) 76 84 Trans/cis ratio 57/43 60/40 Chem. Commun. 3577, 2005 65% ee  71% ee  81% ee Amount of TMS capping Org. Lett. 3, 2493, 2001

Influence of Precapping M C F M C F M C F HMDS + Cu(I) B HMDS toluene Cu(I) Vapor-phase grafting Pre-capping A Post-capping M C F M C F + HMDS M C F Cu(I) C Asymmetric cyclopropanation of styrene Catalyst % Yield Trans/Cis % ee trans % ee cis H 80 68/32 86 84 A 70 59/41 82 79 B 73 64/36 90 87 H C 80 65/35 95 92 Adv. Synth. Catal. 348, 1248, 2006

Asymmetric cyclopropanation of styrene Influence of Precapping MCF Bare MCF Post-capping Cu(I) TMS(0.8)-MCF Pr-1 Post-capping Cu(I) Cu(I) MCF Bare MCF MCF HOMO-Me Pr-2 Pr-3 Asymmetric cyclopropanation of styrene Catalyst Loading (mmolg-1) Run# % Yield Trans:Cis % ee trans % ee cis HOMO-Me 80 71:29 91 87 Pr-1 0.240 1 69 63:37 37 27 2 67 32 Pr-2 0.262 88 83 81 Pr-3 0.066 75 62:38 86 78 Adv. Synth. Catal. 350, 1295, 2008

Fabrication of Immobilized Catalysts Complexation Immobilization Post-capping Pre-capping Cu+ : Si-OH : Si-OTMS : Si-O L

Asymmetric cyclopropanation of styrene Influence of Linker Group TMS(0.8)-MCF Post-capping MCF MP MCF Pr-3 HOMO-MP Asymmetric cyclopropanation of styrene Catalyst Loading amount (mmol/g) Run# Yield (%) Trans:Cis Trans ee% Cis Pr-2 0.120 1 68 70:30 64 2 40 67:33 38 MP 0.148 55 72:28 84 80 58 88 Pr-3 0.066 75 62:38 86 78 HOMO-MP 82 74:26 93 90 Adv. Synth. Catal. 350, 1295, 2008

Blank test by mixing of MCF with Cu(OTf)2 (no ligand) Support = 100 mg, Cu(OTf)2 = 3.6 mg (0.01 mmol) Catalyst Run # Styrene/EDA Yield (%) Trans:Cis MCF:Cu(I) 1 1.5 58 57:43 TMS(0.8)-MCF:Cu(I) 35 63:37 2 53 3 49 67:33 Silanol or siloxane-coordinated cooper can give cyclopropanation products Incomplete complexation Low enantioselectivity Adv. Synth. Catal. 350, 1295, 2008

Influence of Catalyst Loading Amount Loading amount (mmol/g) 0.120 0.262 Trans ee (%) 68 (40)a 88 (91)a Cis ee (%) 64 (38)a 83 (87)a Pr MCF a result from the 2nd run Loading amount (mmol/g) 0.148 0.245 Trans ee (%) 84 93 Cis ee (%) 80 91 MP MCF Catalyst Loading amount (mmol/g) Reaction time (min) Run# Yield (%) Trans/Cis Trans ee% Cis MP 0.507 420 1 81 69/31 94 90 2 77 68/32 180 61 70/30 93 91 63 0.245 75 82 72/28 83 35 4 79 5 Adv. Synth. Catal. 350, 1295, 2008

Packed Bed Reactor Continuous flow reaction Circulating flow reaction Circulating at a high flow rate (5 ml/min) N2 mix Flow rate: 0.2 ml/min MCF Packed Bed Reactor (50 mm  4.6 mm I.D.) Adv. Synth. Catal. 350, 1295, 2008

Circulating Flow-Type Reactor Conditions Reactor = 50 mm x 4.6 mm, Catalyst ~ 240 mg (0.03 mmol) Flow rate = 5.0 ml/min Reaction time per cycle = 75 min Turn over number (TON) per cycle = 100 Total TON = 2000 (20 cycles) Decrease the amount of the reaction medium Trans ee Yield Trans ratio Adv. Synth. Catal. 350, 1295, 2008

Synthesis of Useful Chiral Ingredient + * Cilastatin (dehydropeptidase) MCF Run # Catalyst (mol%) % Yield % ee 1 0.1 90 92 2 Adv. Synth. Catal. 348, 1248, 2006 Run # Catalyst (mol%) % Yield % ee 1a 0.1 90 92 2a 86c 3a 91 4b 5b MCF a Dripping of EDA for 5 hr at 0C and then warm to RT over 14 hr b Dripping of EDA for 5 hr at 5C, stirring at 10C for 90 min, and then warm to RT over 30 min c Overall yield from run #2-5 Adv. Synth. Catal. 350, 1295, 2008

Summary Selectivity and recyclability of silica-supported chiral bisoxazoline-copper(I) were greatly improved by pre-capping, post-capping and a rigid linker group Circulating flow-type reaction system was developed for gas-generating catalytic reactions

Acknowledgments Dr. Jaehong Lim, Dr Han Yu, Ms. Siti Nurhanna Riduan Members of the Nanobiotechnology Group IBN Staff Facilities and Administration Staff IBN, BMRC and A*STAR