Catalytic Asymmetric Intramolecular. Reactions
|
|
|
- Sheryl Nichols
- 6 years ago
- Views:
Transcription
1 Catalytic Asymmetric Intramolecular Pauson-Khand and Pauson-Khand-Type eactions Steven Ballmer CEM 535 Seminar ctober 9, 2008 University of Illinois at Urbana-Champaign pyright 2008 by Steven Ballmer
2 Synthetic Challenges
3 -diated [2+2+1] Cycloaddition (C) 8 C C C C C C hexacarbonyldicobalt alkyne complex + toluene C, 4 h 1 2 cyclopentenone Ph Et Ph Ph Et 43% 33% 45% 28% 23% Side Products C C cyclopentadienyl diketones cobalt (retro Diels-Alder) Pauson and coworkers J. Chem. Soc., Perkin Trans , 975. Pauson and coworkers J. Chem. Soc., Perkin Trans , C C C C C C norbornadiene complexes C C C C
4 Proposed chanism enyne 1 C C C C C C C C alkyne complexation 2C C C C C dissociation 1 1 C C C C C C C C C alkene coordination C C 1 C C C isomerization 1 alkene insertion C C C C C C C C C C 1 alkyl migration +C C C C reductive C 1 (C) coupling 3 C C C C C 1 reductive elimination i 2 (C) 6 1 bicyclic cyclopentenoneclopentenone Magnus and coworkers Tetrahedron 1985, 41, Magnus, P.; Principe, L. M. Tetrahedron Lett. 1985, 26, 4851.
5 chanistic Calculations DFT (VWN/PW91xc) methodology ethylene coordination acetylene complex Pericàs and coworkers Pure Appl. Chem. 2002, 74, 167.
6 Pauson-Khand eaction Promoters
7 Support for Proposed chanism S C C C C C C bishomopropargylic sulfide complex Mixed Ar/N 2 Matrix NM 2, DCM, rt, 5 d S C C C C C 10-6 mbar 12 K isolable pentacarbonyl complex S bishomoallylic sulfide Krafft and coworkers J. Am. Chem. Soc. 1993, 115, Gordon and coworkers J. rganomet. Chem. 1998, 554, 147.
8 MS Support for Proposed chanism Ph C C Ph 2 P C C PPh 2 ESI collision-activated reaction (CA) MS/MS - C dissociation occurs first I dppm m/z = Ph C Ph 2 P C C PPh 2 Ph C C C Ph 2 P PPh 2 Ea = 34 kcal/mol [I dppm --C] - DFT calculations m/z = Ph (B3LYP/LANL2DZ*) [I C dppm --2C] - C E C a = 12 kcal/mol Ph 2 P PPh 2 Gimbert and coworkers rg. Lett. 2003, 5, 4073.
9 -ay Crystal Support for chanism C C C C C C C C C C C hexacarbonyl alkyne complex η 2 -alkene pentacarbonyl alkyne complex Ph 2 (C) 8 TF, rt, 15h Ph C C C C C C C C η 2 -alkene pentacarbonyl alkyne complex (viewed down - bond) Evans and coworkers Angew. Chem. Int. Ed. 2007, 46, 2907.
10 Pauson-Khand egioselectivity
11 Catalytic and Intramolecular Pauson-Khand First Intramolecular First Catalytic Schore, N. E.; Croudace, M. C. J. rg. Chem. 1981, 46, Jeong and coworkers J. Am. Chem. Soc. 1994, 116, 3159.
12 Asymmetric Catalytic Cycle carbon monoxide metallacyclohexenone M P * P * Cl C insertion C * P M * P * Cl metallacyclpentene reductive elimination bicyclic cyclopentenone oxidative addition chiral catalyst Cl M P * P - complexation M Cl P * P catalyst/enyne complex + C - C - C + C C * C M P P Cl enyne M P * P C C pressure-dependence -reaction rate decreases with ithincreased dc pressure -enantioselectivity decreases with increased C pressure Cl
13 eagent-directed Stereocontrol Ph Ph C C P C P C Ph Ph C C Ph Ph P P Ph Ph C ligands not shown pen/closed Quadrants open filled filled open Ph ((S)-BINAP) 2 C 6 P P Ph C ligands not shown isomer Sisomer Ph Ph Ph C C P C P C Ph Ph C C (()-BINAP) 2 C 6 Ph Ph Ph P P Ph C ligands not shown pen/closed Quadrants filled open open filled P P Ph C ligands not shown
14 Substrate-Directed Stereocontrol 1 chair conformer favored olefin rotamer 2 (C) 8 (C) (C) isomer 1 chair conformer disfavored olefin rotamer 2 (C) 8 (C) (C) S isomer
15 Development of balt Catalysts 20 mol % ((S)-BINAP) 2 C 6 DME, reflux, 1 atm C 24 h 24 h 15 h 14 h 14 h 53% yield 31% yield 90% yield 13% yield 60% yield 90% ee 63% ee 0% ee 62% ee 93% ee 2 C 2 C 2 C 2 C TsN TsN 2 C 2 C favored Ph Ph P P Ph Ph Ph Ph P P Ph Ph C ligands not shown disfavored iroi and coworkers Tetrahedron Lett. 2000, 41, 891. iroi and coworkers Tetrahedron: Asymmetry 2000, 11, 797.
16 Development of hodium Catalysts Jeong and coworkers J. Am. Chem. Soc. 2000, 122, 6771.
17 Development of Iridium Catalysts Shibata, T.; Takagi, K. J. Am. Chem. Soc. 2000, 122, 9852.
18 Development of Titanium Catalysts Buchwald and coworkers J. Am. Chem. Soc. 1996, 118, Buchwald and coworkers J. Am. Chem. Soc. 1996, 118,
19 Expansion of Substrate Scope allenynes 2 C 2 C 1 2 dienynes 1 dienenes dienyl cyclopentenones -methylene cyclopentenones 2 C 2 C 1 2 vinyl cyclopentenones vinyl cyclopentanones 1 1 -methylene cyclopentanones 3 2 diene-allenes 3 2 -methylene vinyl cyclopentanones Ph 2 S allenenes S 2 Ph cyclopenteones
20 Bicyclic Dienones from Allenynes C M M M M C bicyclic dienone allenyne -methylene cyclopentenone non-catalytic non-asymmetric S Fe(C) 5,TMAN,TF rt, h (100 W) S S 60% S 15% S 45% S Ph 30% S Ph Fe(C) 3 19% cyclopentadienone iron complex Narasaka, K.; Shibata, T. Chem. Lett. 1994, 315.
21 α-thylene Cyclopentenones from Allenynes C M M M M C bicyclic dienone allenyne -methylene cyclopentenone TMS non-catalytic non-asymmetric Mo(C) 6 (1.2 equiv), DMS Ph, 100 C, 3 h TMS triquinane sesquiterpenes methylenomycin antitumor agents TMS TMS TMS TMS TMS 68% 47% 30% 0% -no cycloaddition -starting material decompostion Brummond and coworkers Tetrahedron Lett. 1995, 36, 2407.
22 Vinyl Cyclopentenones from Dienynes 2 C 2 C 1 2 [hcl(c)(pph 3 ) 2 ], AgSbF 6 DCE, C 2 C 2 C 1 2 1mol%h,Ag 1atmC rt, 14 h 2 C 2 C 89% 2mol%h,Ag TMS 1mol%h,Ag 85% 43% 2atmC 1atmC 2 C 2 C rt, 40 h rt, 12 h 2 C 2 C i-pr i-pr i-pr 1 mol% h, Ag 1atmC rt, 24 h 2 C 2 C 96% 5 mol% h, Ag 1 mol% h, Ag 1atmC 45% 1atmC 42% 2 C rt, 32 h 2 C rt, 30 h 2 C 2 C 2.5 mol% h, Ag 2atmC 40 C, 12 h 2 C 2 C 2.5 mol% h, Ag 86% 2.5 mol% h, Ag 90% 1atmC 2atmC 96% 40 C, 12 h 2 C 40 C, 10 h 2 C 2 C 2 C Wender and coworkers Angew. Chem. Int. Ed. 2003, 42, 1853.
23 Vinyl Cyclopentanones from Dienenes Wender and coworkers J. Am. Chem. Soc. 2004, 126, 5948.
24 α-thylene Cyclopentanones from Diene-Allenes Wender and coworkers Angew. Chem. Int. Ed. 2006, 45, 2459.
25 Bicyclo[5.3.0]decenones from Allenenes Ph 2 S [hcl(c) 2 ] 2,C Ph, 120 C S 2 Ph isomerization to, -unsaturated ketone S 2 Ph Ph 2 S Ph 2 S 5mol%h 10 atm C S 2 Ph 36% 60:40 cis:trans 10 mol% h 10 atm C 47% 60:40 cis:trans 2 C 2 C 2.5 mol% h 5atmC S 2 Ph 49% 15:85 cis:trans 5mol%h 10 atm C 73% 25:75 cis:trans 10 mol% h 10 atm C 82% 35:65 cis:trans S 2 Ph S 2 Ph 2 S 2 Ph TsN 10 mol% h 10 atm C 73% 80:20 cis:trans 10 mol% h 10 atm C 33% 93:7 cis:trans 10 mol% h 10 atm C 30% 100:0 cis:trans 2 C 2 C Ph 2 S 5 mol% [hcl(c) 2 ] 2, 5atmC Ph, 120 C olefin isomerization Ph 2 S 2 C 2 C [2+2] adduct h 2 C 2 C S 2 Ph 68% Mukai and coworkers rg. Lett. 2006, 8, 1217.
26 Applications in Synthesis
27 Synthesis of Isocarbacyclin L-ascorbic acid (C) 6 2 -(2-methyl-3-butyn-2-ol) t 2 l) (C) 6 2 TMS 1 1atmC, 5mol%(C) 6 2 -(2-methyl-3-butyn-2-ol) 10 mol% Et 3 Si, 10 mol% CyN 2, + 1 DME, 65 C, 15 min; 1, reflux,6h Livinghouse conditions (C) 6 2 -alkyne complexes as 2 (C) 8 surrogates TMS 3 51% C 2 33% (C) 3 (C) 3 TMS TMS (C) 2 (C) 2 Saito and coworkers J. rg. Chem. 2004, 69, isocarbacyclin -Prostacyclin (PGI 2 ) analogue -metabolically stable 4
28 Synthesis of Steroidal Skeletons Chung and coworkers J. rg. Chem. 2006, 71, 8264.
29 Synthesis of (-)-Pentalenene Fox and coworkers rg. Lett. 2007, 9, unnatural enantiomer of triquinane natural product -bio precursors to pentalenolactone antiobiotics
30 Synthesis of Tricyclic Sesquiterpenoids TBS MM C 2 5 mol% [hc(dppp) 2 ]Cl, 1atmC,Ph, reflux, 1 h TBS MM C 2 74% hl n MM TBS C2 equatorial, chair Ac 2, TEA, DMAP, DCM, 0 C to rt dimethyl D-tartrate MM 2 C TBS axial, chair hl n MM TBS hl n C 2 equatorial, boat Ac Ac Mukai and coworkers rg. Lett. 2008, 10, isolated from Jatropha neopauciflora
31 nclusion and Future Directions
32 nclusion and Future Directions The Pauson-Khand reaction is a highly versatile and efficient transformation for the synthesis of cyclopentenones. The Pauson-Khand reaction enables construction of complex molecules in a convergent and atom economic fashion from structurally simple precursors. The catalytic, asymmetric, intramolecular variant is highly enabling for the synthesis of stereodefined bicyclic cyclopentenones. eagent-directed stereocontrol absent in context of complex molecule synthesis. Further research must seek out more general conditions for the catalytic, asymmetric, intramolecular Pauson-Khand reaction.
33 Acknowledgements Prof. Scott E. Denmark CEM 535 class Prof. Martin D. Burke Burke Group
CATALYTIC ASYMMETRIC INTRAMOLECULAR PAUSON-KHAND AND PAUSON- KHAND-TYPE REACTIONS
1981. 4 The original protocol for the PKR required superstoichiometric amounts of a metal complex, CATALYTIC ASYMMETRIC INTRAMOLECULAR PAUSON-KHAND AND PAUSON- KHAND-TYPE REACTIONS Reported by Steven G.
Catalytic Asymmetric Pauson-Khand Reaction. Won-jin Chung 02/25/2003
Catalytic Asymmetric Pauson-Khand eaction U. Khand; G.. Knox; P. L. Pauson; W. E. Watts J. Chem. Soc. Chem. Commun. 1971, 36 Won-jin Chung 02/25/2003 The General Pattern of the Pauson-Khand eaction Co
Electrophilic Carbenes
Electrophilic Carbenes The reaction of so-called stabilized diazo compounds with late transition metals produces a metal carbene intermediate that is electrophilic. The most common catalysts are Cu(I)
Additions to Metal-Alkene and -Alkyne Complexes
Additions to tal-alkene and -Alkyne Complexes ecal that alkenes, alkynes and other π-systems can be excellent ligands for transition metals. As a consequence of this binding, the nature of the π-system
JACS ASAP Article: Published 3/12/08. Lei Jiao, Changxia Yuan and Zhi-Xiang Yu. Current Literature: 3/29/08. David Arnold
Tandem h(i)-catalyzed [(5+2)+1] Cycloaddition/Aldol eaction for the Construction of Linear Triquinane Skeleton: Total Syntheses of (+)-irsutene and (+)-1- Desoxyhypnophilin JACS ASAP Article: Published
Molybdenum-Catalyzed Asymmetric Allylic Alkylation
Molybdenum-Catalyzed Asymmetric Allylic Alkylation X MoL n u u * Tommy Bui 9/14/04 Asymmetric Allylic Alkylation from a Synthetic Viewpoint X X M u u * and/or u form a C-C bond with the creation of a new
Asymmetric Catalysis by Lewis Acids and Amines
Asymmetric Catalysis by Lewis Acids and Amines Asymmetric Lewis acid catalysis - Chiral (bisooxazoline) copper (II) complexes - Monodentate Lewis acids: the formyl -bond Amine catalysed reactions Asymmetric
Recent Advances in the Catalytic Pauson Khand-Type Reaction
DOI: 10.1002/adsc.200600328 Recent Advances in the Catalytic Pauson Khand-Type Reaction Takanori Shibata a, * a Department of Chemistry, School of Science and Engineering, Waseda University, Okubo, Shinjuku,
Spiro Monophosphite and Monophosphoramidite Ligand Kit
Spiro Monophosphite and Monophosphoramidite Ligand Kit metals inorganics organometallics catalysts ligands custom synthesis cgm facilities nanomaterials 15-5162 15-5150 15-5156 15-5163 15-5151 15-5157
Highlights of Schmidt Reaction in the Last Ten Years
ighlights of Schmidt eaction in the Last Ten Years Dendrobates histrionicus Jack Liu ov. 18, 2003 Introduction Classical Schmidt reaction of aldehydes and carboxylic acids Classical Schmidt reaction of
Stable gold(iii) catalysts by oxidative addition of a carboncarbon
Stable gold(iii) catalysts by oxidative addition of a carboncarbon bond Chung-Yeh Wu, Takahiro oribe, Christian Borch Jacobsen & F. Dean Toste ature, 517, 449-454 (2015) presented by Ian Crouch Literature
The synthesis of molecules containing quaternary stereogenic centers via the intramolecular asymmetric Heck reaction. Eric Gillis 4/19/07
The synthesis of molecules containing quaternary stereogenic centers via the intramolecular asymmetric Heck reaction Eric Gillis 4/19/07 Quaternary stereocenters in complex small molecules Retrosynthetic
Direct, Catalytic Hydroaminoalkylation of Unactivated Olefins with N-Alkyl Arylamines
Current Literature - May 12, 2007 Direct, Catalytic ydroaminoalkylation of Unactivated lefins with -Alkyl ylamines ' '' Ta[ 2 ] 5 (4-8 mol%), 160-165 o C 24-67h 66-95% ' '' S. B. erzon and J. F. artwig,
Chiral Bronsted Acids as Catalysts
Chiral Bronsted Acids as Catalysts Short Literature Seminar 6/3/08 Dustin aup BIL Derived osphoric Acids - First reported in 1992 as a ligand by irrung and coworkers. 4 h 2 irrung Tet. Lett. 1992, 33,
Zr-Catalyzed Carbometallation
-Catalyzed Carbometallation C C C C ML n C C ML n ML n C C C C ML n ML n C C ML n Wipf Group esearch Topic Seminar Juan Arredondo November 13, 2004 Juan Arredondo @ Wipf Group 1 11/14/2004 Carbometallation
Alkyne Dicobalt Complexes in Organic Chemistry
Alkyne Dicobalt Complexes in Organic Chemistry Sun Baochuan Supervisors: Prof. Yang Prof. Chen Prof. Tang Cobalt - Co From German word kobald - evil spirits Atomic Number: 27 Group: 9 Period: 4 3d 7 4s
Catalytic Reactions in Organic Synthesis
17 April, 2008 Catalytic eactions in rganic Synthesis hodium Complexes and edox Catalysts Koichi AASAKA, Motoki YAMAE, Shunsuke CIBA Division of Chemistry and Biological Chemistry, School of ysical and
Made available courtesy of Wiley-Blackwell: The definitive version is available at
Metal-Catalyzed [2+2+1] Cycloadditions of 1,3-Dienes, Allenes, and CO By: Paul A. Wender, Mitchell P. Croatt, and Nicole M. Deschamps Wender, P. A.; Croatt, M. P.; Deschamps, N. M. Metal-Catalyzed [2+2+1]
Chem 253 Problem Set 7 Due: Friday, December 3, 2004
Chem 253 roblem Set 7 ue: Friday, ecember 3, 2004 Name TF. Starting with the provided starting material, provide a concise synthesis of. You may use any other reagents for your synthesis. It can be assumed
Advanced Organic Chemistry
D. A. Evans, G. Lalic Question of the day: Chemistry 530A TBS Me 2 C Me toluene, 130 C 70% TBS C 2 Me H H Advanced rganic Chemistry Me Lecture 16 Cycloaddition Reactions Diels _ Alder Reaction Photochemical
Asymmetric Synthesis of Medium-Sized Rings by Intramolecular Au(I)-Catalyzed Cyclopropanation
Asymmetric Synthesis of Medium-Sized ings by Intramolecular Au(I)-Catalyzed Cyclopropanation 1 2 Iain D. G. Watson, Stefanie itter, and F. Dean Toste JACS, ASAP, 1/22/2009 DI: 10.1021/ja8085005 2.5 mol%
Chiral Brønsted Acid Catalysis
Chiral Brønsted Acid Catalysis Aryl Aryl Aryl Aryl S CF 3 2 P Fe CF 3 CF 3 2 Jack Liu ov. 16, 2004 CF 3 Introduction Chiral Brønsted acid catalysis in nature: enzymes and peptides Chiral Brønsted acid
Chiral Catalyst II. Palladium Catalysed Allylic Displacement ( -allyl complexes) 1. L n Pd(0) 2. Nuc
Chiral Catalyst II ast lecture we looked at asymmetric catalysis for oxidation and reduction Many other organic transformations, this has led to much investigation Today we will look at some others...
Total synthesis of Spongistatin
Literature Semminar 1. Introduction: Total synthesis of Spongistatin Chen Zhihua (M2) Isolation: Pettit et al. J. rg. Chem. 1993, 58, 1302. Kitagawa et al. Tetrahedron Lett. 1993, 34, 1993. Fusetani et
Short Literature Presentation 10/4/2010 Erika A. Crane
Copper-Catalyzed Enantioselective Synthesis of trans-1- Alkyl-2-substituted Cyclopropanes via Tandem Conjugate Additions-Intramolecular Enolate Trapping artog, T. D.; Rudolph, A.; Macia B.; Minnaard, A.
Functionalization of C(sp 3 ) H Bonds Using a Transient Directing Group
Literature eport Functionalization of C(sp 3 ) Bonds Using a Transient Directing Group eporter: Mu-Wang Chen Checker: Yue Ji Date: 2016-04-05 Yu, J.-Q. et al. Science 2016, 351, 252-256. Scripps esearch
VI. Metal alkyls from oxidative addition / insertion
V. Metal alkyls from oxidative addition / insertion A. Carbonylation - C insertion very facile, metal acyls easily cleaved, all substrates which undergo oxidative addition can in principle be carbonylated.
Branched-Regioselective Hydroformylation with Catalytic Amounts of a Reversibly Bound Directing Group
1/12 Branched-egioselective ydroformylation with Catalytic Amounts of a eversibly Bound Directing Group h(i)/me C/ 2 MS 4A branched major by Christian U. Grünanger and Bernhard Breit Angew. Chem. Int.
Nickel-Catalyzed Three-Component [3+2+2] Cocyclization of Ethyl Cyclopropylideneacetate and Alkynes
![Nickel-Catalyzed Three-Component [3+2+2] Cocyclization of Ethyl Cyclopropylideneacetate and Alkynes](/thumbs/77/74720708.jpg "Nickel-Catalyzed Three-Component [3+2+2] Cocyclization of Ethyl Cyclopropylideneacetate and Alkynes")
Nickel-Catalyzed Three-Component [3+2+2] Cocyclization of Ethyl Cyclopropylideneacetate and Alkynes Selective Synthesis of Multisubstituted Cycloheptadienes 1 2 Cat. Ni 0 1 2 Komagawa, S.; Saito, S. Angew.
The Synthesis of Molecules Containing Quaternary Stereogenic Centers via the Intramolecular Asymmetric Heck Reaction
The Synthesis of Molecules Containing Quaternary Stereogenic Centers via the Intramolecular Asymmetric Heck Reaction Reported by Eric P. Gillis April 19, 2007 INTRODUCTION The enantioselective synthesis
Corey-Bakshi. Bakshi-Shibata Reduction. Name Reaction Nilanjana Majumdar
Corey-Bakshi Bakshi-Shibata Reduction Name Reaction Nilanjana Majumdar 02.27.09 utline Introduction Background CBS Reaction Application to Synthesis Introduction Born: 12 th July, 1928 in Methuen, Massachusetts,
"-Amino Acids: Function and Synthesis
"-Amino Acids: Function and Synthesis # Conformations of "-Peptides # Biological Significance # Asymmetric Synthesis Sean Brown MacMillan Group eting ovember 14, 2001 Lead eferences: Cheng,. P.; Gellman,
Cascade Reactions Involving Pauson Khand and Related Processes
Top Organomet Chem (2006) 19: 207 257 DOI 10.1007/3418_008 Springer-Verlag Berlin Heidelberg 2006 Published online: 12 April 2006 Cascade Reactions Involving Pauson Khand and Related Processes Javier Pérez-Castells
Synthesis of Resorcinylic Macrolides
Synthesis of Resorcinylic Macrolides X H H H H Cl X= Radicicol (1) X= CH2 Cycloproparadicicol (2) Danishefsky, S. J. J. Am. Chem. Soc. 2004, 126, ASAP Danishefsky, S. J. rg. Lett. 2004, 6, 413-416 Danishefsky,
Recent Advances in the Chemistry of Alleneamides. Denmark Group Meeting Nate Duncan-Gould
Recent Advances in the hemistry of Alleneamides Denmark Group eting ate Duncan-Gould 9-25-07 allene The Structure allenamine ummulenes!!! X X X!!! X X ummulene omparison of M s FM at PM3 level M LUM alculated
Catalytic Asymmetric Acyl Halide-Aldehyde Cyclocondensation Reactions of Substituted Ketenes
Catalytic Asymmetric Acyl Halide-Aldehyde Cyclocondensation eactions of Substituted Ketenes Scott G. elson, Cheng Zhu, and Xiaoqiang Shen J. Am. Chem Soc. 2004, 126, 14-15. Michael C. Myers, Literature
Carbonyl Ylide Cycloadditions
Carbonyl Ylide Cycloadditions cond. icholas Anderson Denmark Group eting 07/13/10 Carbonyl Ylides Uncharged 1,3-Dipole Conjugated π-system ighly reactive on-isolable Generate in-situ Carbonyl Ylide Stability
Recent Advancements In The [2+2+2] Cycloaddition. Brandon Dutcher January 17, 2007 Michigan State University
![Recent Advancements In The [2+2+2] Cycloaddition. Brandon Dutcher January 17, 2007 Michigan State University](/thumbs/72/66469911.jpg "Recent Advancements In The [2+2+2] Cycloaddition. Brandon Dutcher January 17, 2007 Michigan State University")
ecent Advancements In The [2+2+2] Cycloaddition Brandon Dutcher January 17, 2007 ichigan tate University utline verview of [2+2+2] cycloaddition chanism of the [2+2+2] cycloaddition Issues with selectivity
sp 3 C-H Alkylation with Olefins Yan Xu Dec. 3, 2014
sp 3 C-H Alkylation with Olefins, Yan Xu Dec. 3, 2014 1) sp 3 C-H Alkylation via Directed C-H activation 2) Hydroaminoalkylation (still via C-H activation) 3) Hydrohydroxyalkylation (via radical chemistry)
Enantioselective Borylations. David Kornfilt Denmark Group Meeting Sept. 14 th 2010
Enantioselective Borylations David Kornfilt Denmark Group Meeting Sept. 14 th 2010 30.000-foot View Enantioenriched Organoboranes What to do with them Crudden C. M. et. al., Eur. J. Org. Chem. 2003, 46
Palladium-Catalyzed Asymmetric Benzylic Alkylation Reactions
Palladium-Catalyzed Asymmetric Benzylic Alkylation Reactions Reporter: Hong-Qiang Shen Checker: Cong Liu Date: 2016/07/12 Masahiro Miura et al. Angew. Chem. Int. Ed. 2016, 55, 6973. Masahiro Miura Osaka
Chapter 5 Three and Four-Membered Ring Systems
Chapter 5 Three and Four-mbered ing ystems 5.1 Aziridines Aziridines are good alkylating agents because of their tendency to undergo ring-opening reaction with nucleophiles 例 mitomycin C antibiotic and
Rhenium-Catalyzed Synthesis of Multisubstituted Aromatic Compounds via C-C Single-Bond Cleavage
henium-catalyzed Synthesis of Multisubstituted Aromatic Compounds via C-C Single-Bond Cleavage Kuninobu, Y.; Takata,.; Kawata, A.; Takai, K. rg. Lett. ASAP Et 5 6 cat. [ebr(c) 3 (thf)] 2 5 6 Current Literature
Organic Cumulative Exam October 13, 2016
rganic Cumulative Exam ctober 3, 206 Answer only three of the five questions. o more than three question answers will be graded and any work not to be considered must be clearly marked as such. Clearly
Carbenes and Carbene Complexes I Introduction
Carbenes and Carbene Complexes I Introduction A very interesting (honest) class of radical-like molecules Steadily becoming more important as they find far more synthetic applications We will primarily
Regioselective Reductive Cross-Coupling Reaction
Lit. Seminar. 2010. 6.16 Shinsuke Mouri (D3) Regioselective Reductive Cross-Coupling Reaction Glenn C. Micalizio obtained a Ph.D. at the University of Michigan in 2001 under the supervision of Professor
Denmark Group Meeting. & Electrophilic rearrangement of amides
Denmark Group Meeting Palladium catalyzed Dearomatizationeaction & Electrophilic rearrangement of amides 11 th Bo Peng th Feb. 2014 1 https://maps.google.com 2 Palladium catalyzed Dearomatization eaction
Functionalization of terminal olefins via H migratory insertion /reductive elimination sequence Hydrogenation
M.C. White, Chem 153 verview -282- Week of ovember 11, 2002 Functionalization of terminal olefins via migratory insertion /reductive elimination sequence ydrogenation ML n E ydrosilylation Si 3 Si 3 ML
Solvias (R)-MeO-BIPHEP Ligand Kit
metals inorganics organometallics catalysts ligands custom synthesis cgm facilities nanomaterials Catalog # 96-3655 Solvias ()- and (S)-Me BIE Ligand Kits for asymmetric hydrogenation and other catalytic
Stereoselective Synthesis of Configurationally Stable Functionalized Ethano-Bridged Tröger Bases
Stereoselective Synthesis of Configurationally Stable Functionalized Ethano-Bridged Tröger Bases Michon, C.; Sharma, A.; Bernardinelli, G.; Francotte, E.; Lacour, J. Chem. Commun., 2010, 46, 2206-2208
Strained Molecules in Organic Synthesis
Strained Molecules in rganic Synthesis 0. Introduction ~ featuring on three-membered rings ~ Tatsuya itabaru (M) Lit. Seminar 08068 for cyclobutadienes : see Mr. Yamatsugu's Lit. Sem. 069 eat of Formation
The Allenic Pauson Khand Reaction in Synthesis
The Allenic Pauson Khand Reaction in Synthesis Benito Alcaide* [a] and Pedro Almendros* [b] Keywords: Allenes / Carbonylation / Cycloaddition / Organometallics / Synthetic methods The Pauson Khand (PK)
Name: CHEM 633: Advanced Organic Chemistry: Physical Final Exam. Please answer the following questions clearly and concisely.
Name: 1 CEM 633: Advanced rganic Chemistry: Physical Final Exam Please answer the following questions clearly and concisely. You may write your answers in the space provided and/or on additional pages.
Mechanism Problem. 1. NaH allyl bromide, THF N H
Mechanism Problem 1. a allyl bromide, TF 2. 9-BB (1.2 equiv), TF, rt; ame (1.2 equiv); t-buli (2.4 equiv), TMEDA (2.4 equiv) 30 to rt; allyl bromide; 30% 2 2, aq. a, 0 C (58% yield) Mechanism Problem 9-BB
Olefin Metathesis ROMP. L n Ru= ROMP n RCM. dilute
lefin Metathesis MP: ing-opening metathesis polymerization Thermodynamically favored for 3,4, 8, larger ring systems Bridging groups (bicyclic olefins) make ΔG polymerization more favorable as a result
Chiral Catalysis. Chiral Catalyst. Substrate. Chiral Catalyst
Chiral Catalysis Chiral (stoichiometric) reagents are a very important class of compound but... eed a stoichiometric quantity of the chiral component Unless it is cheap or recoverable this is not very
Metal-catalyzed asymmetric hetero-diels-alder reactions of unactivated dienes with glyoxylates
Pure & Appl. Chern., Vol. 70, No. 5, pp. 11 17-1 122, 1998. Printed in Great Britain. (0 1998 IUPAC Metal-catalyzed asymmetric hetero-diels-alder reactions of unactivated dienes with glyoxylates Mogens
Negishi Coupling of Secondary Alkylzinc Halides with Aryl Bromides and Chlorides
Negishi Coupling of Secondary Alkylzinc alides with Aryl Bromides and Chlorides X X = Br, Cl 2 1 ZnBr 1, 2 = Alkyl Cat. Pd(OAc) 2 Ligand TF/Toluene rt or 60 o C 1 2 J. Am. Chem. Soc. 2009, ASAP Article
Chapter 4 Electrophilic Addition to Carbon Carbon Multiple Bonds 1. Addition of H X 2. Addition of H OH and addition of Y X 3. Addition to allene and
Chapter 4 Electrophilic Addition to Carbon Carbon Multiple Bonds 1. Addition of X 2. Addition of and addition of Y X 3. Addition to allene and alkyne 4. Substitution at α-carbon 5. eactions via organoborane
Copper-Catalyzed Reaction of Alkyl Halides with Cyclopentadienylmagnesium Reagent
Copper-Catalyzed eaction of Alkyl Halides with Cyclopentadienylmagnesium eagent Mg 1) cat. Cu(Tf) 2 i Pr 2, 25 o C, 3 h 2) H 2, Pt 2 Masahiro Sai, Hidenori Someya, Hideki Yorimitsu, and Koichiro shima
Lewis Base Catalysis: the Aldol Reaction (Scott Denmark) Tom Blaisdell Friday, January 17 th 2014 Topic Talk
Lewis Base Catalysis: the Aldol eaction (Scott Denmark) Tom Blaisdell Friday, January 17 th 2014 Topic Talk Scott E. Denmark 1975 - S.B. in Chemistry MIT (ichard. olm and Daniel S. Kemp) 1980 - D.Sc in
ACTIVATION OF C H BONDS BY LOW-VALENT METAL COMPLEXES ( THE ORGANOMETALLIC CHEMISTRY )
CHAPTER IV ACTIVATION OF C H BONDS BY LOW-VALENT METAL COMPLEXES ( THE ORGANOMETALLIC CHEMISTRY ) n the end of the 1960s the leading specialist in homogeneous catalysis Jack Halpern wrote [1]: to develop
Titanacyclopropanes as versatile intermediates for carbon carbon bond formation in reactions with unsaturated compounds*
Pure Appl. Chem., Vol. 72, No. 9, pp. 1715 1719, 2000. 2000 IUPAC Titanacyclopropanes as versatile intermediates for carbon carbon bond formation in reactions with unsaturated compounds* O. G. Kulinkovich
Shi Asymmetric Epoxidation
Shi Asymmetric Epoxidation Chiral dioxirane strategy: R 3 + 1 xone, ph 10.5, K 2 C 3, H 2, C R 3 formed in situ catalyst (10-20 mol%) is prepared from D-fructose, and its enantiomer from L-sorbose oxone,
1. Theoretical Investigation of Mechanisms and Stereoselectivities of Synthetic Organic Reactions
1. Theoretical Investigation of Mechanisms and Stereoselectivities of Synthetic Organic Reactions 2. Copper Catalyzed One-Pot Synthesis of Multisubstituted Quinolinones Hao Wang Denmark Group Presentation
Intramolecular Huisgen-Type Cyclization of Platinum-Bound Pyrylium Ions with Alkenes and Subsequent Insertion into a Benzylic C-H Bond
Intramolecular uisgen-type Cyclization of Platinum-Bound Pyrylium Ions with Alkenes and Subsequent Insertion into a Benzylic C- Bond Chang o h,* Ji o Lee, Su Jin Lee, Jae Il Kim, and Chang Seop ong Department
Non-Linear Effects in Asymmetric Catalysis: A Useful Tool in Understanding Reaction Mechanisms. Group Meeting Aaron Bailey 12 May 2009
Non-Linear Effects in Asymmetric Catalysis: A Useful Tool in Understanding Reaction chanisms Group eting Aaron Bailey 12 May 2009 What is a Non-Linear Effect? In asymmetric catalysis, the ee (er) of the
Copper-Catalyzed Synthesis of Esters from Ketones. Alkyl Group as a Leaving Group.
Copper-Catalyzed Synthesis of Esters from Ketones. Alkyl Group as a Leaving Group. akatani, Y.; Koizumi, Y.; Yamasaki, R.; Saito, S. rg. Lett. 2008, 10, 2067-2070. An Annulation Reaction for the Synthesis
Rhodium Catalyzed Alkyl C-H Insertion Reactions
Rhodium Catalyzed Alkyl C-H Insertion Reactions Rh Rh Jeff Kallemeyn 5/17/05 1. Cyclopropanation The Versatile and Reactive Rhodium Carbene R + Et Rh 2 (Ac) 4 R C 2 Et N 2 2. [2,3] sigmatropic rearrangement
Journal Club Presentation by Remond Moningka 04/17/2006
β-alkyl-α-allylation of Michael Acceptors through the Palladium-Catalyzed Three-Component Coupling between Allylic Substrate, Trialkylboranes, and Activated lefins Yoshinori Yamamoto, et al. J. rg. Chem.
Development of Chiral Phosphine Olefin Ligands and Their Use in Asymmetric Catalysis
Development of Chiral osphine lefin Ligands and Their Use in Asymmetric Catalysis 2 Wei-Liang Duan July 31, 2007 Research Works in Hayashi Group, Kyoto University (ct, 2003 Mar, 2007) Conventional Chiral
Wilkinson s other (ruthenium) catalyst
Wilkinson s other (ruthenium) catalyst Cl 3 ; 2 h 3, reflux 3h h 3 Cl h 3 h Cl 3 Good catalyst especially for 2 1-alkenes 2, base toluene Cl h 3 h 3 h 3 Et 3 Cl h 3 Cl h 3 h 3 R h 3 h 3 Cl h 3 R RC 2 C
Research Summary. Lei Jiao, Ph.D. in Chemistry
esearch Summary Lei Jiao, Ph.D. in Chemistry My research focused on three aspects of organic chemistry: developing new reactions, mechanistic study on organic reactions (both experimental and computational),
When something goes wrong. Goya: Mother showing her derformed child to two women Louvre, Paris
1 ew Catalytic Asymmestric eactions Karl Anker Jørgensen Danish ational eserach Foundation: Center for Catalysis Department of Chemistry, Aarhus University Denmark kaj@chem.au.dk When something goes wrong
i-pr 2 Zn CHO N Sato, I.; Sugie, R.; Matsueda, Y.; Furumura, Y.; Soai, K. Angew. Chem., Int. Ed. Engl. 2004, 43, 4490
Asymmetric Synthesis Utilizing Circularly Polarized Light Mediated by the otoequilibration of Chiral lefins in Conjuction with Asymmetric Autocatalysis l-cpl r-cpl (S) () Sato, I.; Sugie,.; Matsueda, Y.;
Stereoselective reactions of the carbonyl group
1 Stereoselective reactions of the carbonyl group We have seen many examples of substrate control in nucleophilic addition to the carbonyl group (Felkin-Ahn & chelation control) If molecule does not contain
Enantioselective Synthesis of Pactamycin, a Complex Antitumor Antibiotic
Journal Club (3) Tomoya akamura Enantioselective Synthesis of Pactamycin, a Complex Antitumor Antibiotic Justin T. Malinowski, Robert J. Sharpe, Jeffrey S. Johnson Science 03, 30, 80 8.. Introduction -.
The aldol reaction with metal enolates proceeds by a chair-like, pericyclic process: favored. disfavored. favored. disfavored
The aldol reaction with metal enolates proceeds by a chair-like, pericyclic process: Z-enolates: M 2 M 2 syn 2 C 2 favored 2 M 2 anti disfavored E-enolates: M 2 2 C 3 C 3 C 2 favored 2 M M disfavored In
Synthesis of Substituted 1,4-Dienes by Direct Alkylation of Allylic Alcohols Kolundzic, F.; Micalizio, G. C. J. Am. Chem. Soc. 2007, 129,
Synthesis of Substituted 1,4-Dienes by Direct Alkylation of Allylic Alcohols Kolundzic, F.; Micalizio, G. C. J. Am. Chem. Soc. 2007, 129, 15112-15113. Total Synthesis and Structure Elucidation of (+)-orbasin
Keisuke Suzuki. Baran lab Group Meeting 6/11/16. Shigenobu Umemiya. Akira Suzuki. Takanori Suzuki (Hokkaido University)
197.D., Teruaki Mukaiyama, University of Tokyo 193 Assistant Professor, Keio University 197 Lecturer, Keio University 199 Assocate Professor, Keio University 1990 Visiting Professor, ET 1994 ull Professor,
Direct Oxidative Heck Cyclizations: Intramolecular Fujiwara-Moritani Arylations for the Synthesis of Functionalized Benzofurans and Dihydrobenzofurans
Direct xidative eck Cyclizations: Intramolecular Fujiwara-Moritani Arylations for the Synthesis of Functionalized Benzofurans and Dihydrobenzofurans by Zhang,.; Ferreira, E. M.; Stoltz, B. M. Angewandte
Catalytic Asymmetric [4+1] Annulation of Sulfur Ylides with Copper Allenylidene Intermediates. Reporter: Jie Wang Checker: Shubo Hu Date: 2016/08/02
![Catalytic Asymmetric [4+1] Annulation of Sulfur Ylides with Copper Allenylidene Intermediates. Reporter: Jie Wang Checker: Shubo Hu Date: 2016/08/02](/thumbs/93/114018431.jpg "Catalytic Asymmetric [4+1] Annulation of Sulfur Ylides with Copper Allenylidene Intermediates. Reporter: Jie Wang Checker: Shubo Hu Date: 2016/08/02")
Catalytic Asymmetric [4+1] Annulation of Sulfur Ylides with Copper Allenylidene Intermediates Reporter: Jie Wang Checker: Shubo Hu Date: 2016/08/02 Xiao, W.-J. et al. J. Am. Chem. Soc. 2016, 138, 8360.
Discussion Addendum for: Nickel-catalyzed Homoallylation of Aldehydes with 1,3-Dienes
DI:10.15227/orgsyn.090.0105 Discussion Addendum for: Nickel-catalyzed Homoallylation of Aldehydes with 1,3-Dienes CH anti:syn = 30:1 CH cat. Et 2 Zn anti:syn = 30:1 Prepared by Masanari Kimura.* 1 riginal
Stereoselective Organic Synthesis
Stereoselective rganic Synthesis Prabhat Arya Professor and Leader, Chemical Biology Program Dean, Academic Affairs, Institute of Life Sciences (An Associate Institute of University of yderabad Supported
Asymmetric Radical Reactions. Zhen Liu 08/30/2018
Asymmetric adical eactions Zhen Liu 08/30/2018 Contents Introduction eactions Using Chiral Auxiliary Chiral Lewis Acid-diated eactions Transition tal-catalyzed eactions eactions Using Chiral rganocatalysts
CYCLOBUTADIENE IN ORGANIC SYNTHESIS
Lit. Seminar 061129 CYCLBUTADIENE IN GANIC SYNTESIS Usage of Unstable Intermediate: Cyclobutadiene as A Case 0. Introduction (C) 3 Fe 2 steps Kenzo YAMATSUGU (M2) (+)-Asteriscanolide difficulty to use
Metal Catalyzed Outer Sphere Alkylations of Unactivated Olefins and Alkynes
Metal Catalyzed uter Sphere Alkylations of Unactivated lefins and Alkynes Stephen Goble rganic Super-Group Meeting Literature Presentation ctober 6, 2004 1 utline I. Background Introduction to Carbometallation
Transition Metal Catalyzed Carbon-Carbon Bond Activation
literature seminar 2 H. Mitsunuma(M1) 2010/09/08 Transition tal Catalyzed Carbon-Carbon Bond Activation 0. Introduction Currently, selective C-H and C-C bond activation by transition metal complexes has
Chiral Proton Catalysis in Organic Synthesis. Samantha M. Frawley Organic Seminar September 14 th, 2005
Chiral Proton Catalysis in rganic Synthesis Samantha M. Frawley rganic Seminar September 14 th, 2005 Seminar utline Introduction Lewis Acid-assisted Chiral Brønsted Acids Enantioselective protonation for
Synthetic Methodology. Using Tertiary Phosphines. as Nucleophilic Catalysts
Synthetic Methodology Using Tertiary osphines as Nucleophilic Catalysts 1 3 2 u 2 (P 3 ) 3 4 1 2 D. Ma, X. Lu 1988 1 2 Pd 2 (dba) 3.CCl 3 /P 3 /Ac or Pd(Ac) 2 /P 3 1 2 B. M. Trost 1988 1 3 2 u 2 (P 3 )
Chiral Supramolecular Catalyst for Asymmetric Reaction
Chiral Supramolecular Catalyst for Asymmetric Reaction 2017/1/21 (Sat.) Literature Seminar Taiki Fujita (B4) 1 Introduction Rational design of chiral ligands remains very difficult. Conventional chiral
O + k 2. H(D) Ar. MeO H(D) rate-determining. step?
ame: CEM 633: Advanced rganic Chem: ysical Problem Set 6 (Due Thurs, 12/8/16) Please do not look up references until after you turn in the problem set unless otherwise noted. For the following problems,
Bifunctional Asymmetric Catalysts: Design and Applications. Junqi Li CHEM Sep 2010
Bifunctional Asymmetric Catalysts: Design and Applications Junqi Li CHEM 535 27 Sep 2010 Enzyme Catalysis vs Small-Molecule Catalysis Bronsted acid Lewis acid Lewis acid Bronsted base Activation of both
Dual enantioselective control by heterocycles of (S)-indoline derivatives*
Pure Appl. Chem., Vol. 77, No. 12, pp. 2053 2059, 2005. DOI: 10.1351/pac200577122053 2005 IUPAC Dual enantioselective control by heterocycles of (S)-indoline derivatives* Yong Hae Kim, Doo Young Jung,
Non-Metathesis Ruthenium-Catalyzed Reactions for Organic Synthesis
on-tathesis thenium-catalyzed eactions for rganic Synthesis Tristan Lambert MacMillan Group eting May 23, 2002 I. Properties of thenium II. eductions III. xidations IV. Isomerizations V. C-C bond forming
Lecture 6: Transition-Metal Catalysed C-C Bond Formation
Lecture 6: Transition-Metal Catalysed C-C Bond Formation (a) Asymmetric allylic substitution 1 u - d u (b) Asymmetric eck reaction 2 3 Ar- d (0) Ar 2 3 (c) Asymmetric olefin metathesis alladium π-allyl
Hydroboration. Carreira: Chapter 7
ydroboration Carreira: Chapter 7 ydroboration of alkenes/alkynes is one of the most versatile reactions available. Most commonly, the resulting alkyl borane intermediates are not isolated, but are used
Supporting Information. Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2007
Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2007 Electronic and Steric Effects of Atropisomeric Ligands SYNPHS, and DIFLUPHS vs BINAPs in h(i)-catalyzed Asymmetric
Iridium-Catalyzed Hydrogenation with Chiral P,N Ligands
Iridium-Catalyzed Hydrogenation with Chiral P, Ligands 贾佳 utline Brief Introduction Hydrogenation of C=C Bonds Hydrogenation of C= Bonds Hydrogenation of C= Bonds Conclusion Brief Introduction First example
Nickel-Catalyzed Cycloadditions
ckel-catalyzed Cycloadditions Tristan ambert MacMillan Group eting January 31, 001 Properties of nickel Introduction to metal-catalyzed cycloadditions ckel-catalyzed cycloadditions eview of metal-catalyzed