Hypervalent (III) iodine chemistry
|
|
|
- Milton Pearson
- 5 years ago
- Views:
Transcription
1 Hypervalent (III) iodine chemistry Alcohol and phenol oxydation by 1 Diacetyliodobenzene (DIB)
2 H NH PhI(2.2 eq.) H 2,12h,rt 74% NH chiai, M. et al., Chem. Pharm. Bull. 2004,
3 Summary Generalities Brief history of hypervalent iodine Structure and bonding Classification Most common reagents bjectives Reactivity towards alcohols Reactivity towards phenols Reactivity towards phenol ethers Short glimpse at the rest of iodine chemistry 3
4 About Iodine rganohypervalent iodine: Varvoglis, A., Synthesis 1984, Stang, P. J. and Zhdankin, V. V., Chem. Rev. 1996, Stang, P. J. and Zhdankin, V. V., Chem. Rev. 2002, Stang, P. J. and Zhdankin, V. V., Chem. Rev. 2008, Moriarty, R. M., J. rg. Chem. 2005, Key words about hypervalent iodine: xydation, Umpolung 4
5 A brief history of (hypervalent) iodine 1811 iodine was first isolated by B. Courtois 1813 J. L. Gay Lussac names it iodine 1886 Willgerodt prepared the first polyvalent organic iodine PhICl Willgerodt publishes Die rganischen Verbingungen mit Mehrwertigen Jod commercialisation of iodosylbenzene, Dess-Martin periodinane and [Bis(acetyloxy)iodo]benzene 5
6 Structure and bonding 3 parts: Iodine central atom Carbon ligand Apical ligands 6
7 rganohypervalent (III) Iodine families Willgerodt, C. et coll Boeeseken et coll Koser, G. F. Wettach, R. H Godstein, H. Grampoloff, A. V Hartman, M. et coll Wittig, R. et coll Tyrra, W. Naumann, D. 1989
8 Most common reagents iodobenzene dichloride Cl I Cl Moriarty's reagent Me I Me Iodosylbenzene iodobenzene difluoride F I F Diacetoxy Iodobenzene (DIB) Ac I Ac I I I oligomer Koser's reagent H I Ts Ditrifluoroacetoxy Iodobenzene F 3 C I CF 3 Togni's reagent CF 3 I 8
9 Why Alcohol and phenol oxydation by Diacetyliodobenzene (DIB)? 9
10 Diacyloxy iodobenzene Diacetoxy iodobenzene (DIB): Alternative names: Iodobenzene diacetate, (Diacetoxyiodo)benzene, Iodosobenzene diacetate, PIA, PIDA CAS: Price: Sigma-Aldrich 25 g / 63.90, Acros rganics 25 g / Melting point: C Aspect: white powder Risks: Harmful, irritant Bis(trifluoacetyloxy)iodobenzene (BTI): CAS: Price: Sigma-Aldrich 25 g / , Acros rganics 50 g / Melting point: C Aspect: white powder Risks: Irritant CF 3 I =PhI(CCF 3 ) 2 CF 3 10
11 Diacyloxy iodoarenes Preparation: xydation of iodoarenes in the presence of a carboxylic acid (1) Ligand exchange of the readily available DIB (2) 11
12 Reactivity towards alcohols Examples: G. Piancatelli et al., J. rg. Chem., 1997,
13 Reactivity towards alcohols Suggested mechanism: 13
14 Reactivity towards alcohols Advantages: Selective method Very mild reagent Easy purification Reaction scope: Primary > secondary alcohol No double bond isomerisation Compatible with various oxydation-sensitive functionnalities 14
15 Reactivity towards alcohols Primary alcohols can also be converted to esters and lactones H I 2 (10mol%) DIB(1.1 eq.) MeCN,rt,2h 97% H I 2 (10mol%) DIB(1.1 eq.) MeCN,rt,3h 83% H H I 2 (10mol%) DIB(1.1 eq.) MeH,rt,5h 82% Karade, N. N., Synlett 2005,
16 Reactivity towards alcohols Boc N H H TEMP(0.2 eq.) DIB(3.2 eq.) DCM(0.2M),rt,3.5h 95% Boc N C. J. Forsyth et al., Tetrahedron Lett. 2003, H H H TEMP(0.2 eq.) DIB(5eq.), DCM,rt,5h,94% H Hale, K. J., rg. Lett. 2007,
17 Reactivity towards phenols Examples: H PhI(Ac) 2 MeH,45mn, 0 C,99% Pelter,A.etal.,J.Chem.Soc.,PerkinTrans.11993, H PhI(CCF 3 ) 2 Water/MeCN, 0 C,67% H Taylor,R.J.K.etal.,J.Chem.Soc.,PerkinTrans.11994,
18 Reactivity towards phenols H PhIX 2 -HX Ph I X -HX Nu + Nu H Nu H PhIX 2 Ph I X -PhI -X - Nu + Nu Nu 18
19 Reactivity towards phenols ortho-substitution Regioselectivity Requires a group stabilizing Wheland s intermediate H PhI(Ac) 2 MeH, rt R R=H,Alk,C()Alk,C()Alk, Cl,Br,F,CN R Nucleophile: Solvent rganoiodine ligand Intramolecular moiety Nucleophile added to the reaction mixture 19
20 20
21 Reactivity towards phenols para-substitution Much more examples in the litterature: product is a prochiral highly functionnalizable molecule 21
22 Reactivity towards phenols para-substitution H PIFA,Py.(HF) x DCM, rt, 30mn,66% F Jouannetaud, M.-P. et al., Tetrahedron Lett. 1994, H DIB MeCN/H 2 0 C,30mn 43% H Glover,S.A.etal.,J.Am.Chem.Soc.2004, H PIFA, MeCN TFA,rt,10mn 86% Ciufolini,M.A.etal.,J.rg.Chem.2008, N H
23 Reactivity towards phenols carbon-carbon bond formation H N Pyridine, PIFA H N H MeCN,rt,30mn 42% Kita, Y. et al., Tetrahedron Lett., 1989, H PIFA Me N Me Me -40 C,5mn 54% N Me TMS TMS Kita,Y.etal.,J.rg.Chem.,1996, H N DMAP, CuS 4, 5H 2 DIB EtH,0 C,70mn 88% N 23 Zhang, H. et al., Chem. Comm., 2011,
24 Reactivity towards phenols carbon-carbon bond formation 24
25 Reactivity towards phenols carbon-carbon bond formation 25
26 Reactivity towards phenols catalysis 26
27 Reactivity towards phenols chirality H H DIB(1eq.),NaHC 3 TFE,-35 C + >95:5 MeMgBr THF,-78 C H TsH.H 2 Acetone H H H d.r.>95:5 54%over2steps e.r. 93:7 56% (+)-biscarvacrol Quideau, S. et al., Angew. Chem. Int. Ed. 2008,
28 Reactivity towards phenols chirality 28
29 Reactivity towards phenols chirality 29
30 Reactivity towards phenols tandem oxydation/diels-alder reactions Shortcoming: some product dimerise by Diels-Alder reactions 30
31 Reactivity towards phenols tandem oxydation/diels-alder reactions S N H H PhI(Ac) 2 TFA,10mn, rt, 60% N S 2 S NH H DIB TFA, rt N S 2 Toluene addition Heat 39% H H S 2 Ciufolini, M. A. et al., Chem. Eur. J. 2010,
32 Reactivity towards phenol ethers R = alkyl, alkoxy, halogen, etc Nu = external or internal nucleophilic group 32
33 Reactivity towards phenol ethers 33
34 Moriarty oxydation A glimpse of iodine (III) chemistry Ph DIB KH MeH rt,2h Me Ph Me H Frye,S.V.etal.,J.Am.Chem.Soc.,1992, or Ph H Depending on the work-up Me Me N PhI(2.2 eq.), Bu 4 NI(0.3eq) H 2,rt,2h,96% Me Me Lee, S.-S. et al., Helv. Chim. Acta 2002, N PhI(H)Ts, 95% MeH, rt, 20mn,84% Koser, G. F. et al., Tetrahedron Lett. 2004, 6159 DIB(2.3 eq.) KH(3.0 eq.) 1)LDA(1.2eq.) ClC 2 Me(3.0eq.) Et 2,-78 C,79% 1)P 2 5 MeS 3 H,rt 94% MeH -5 C,40% 2)KH MeH-H 2,rt 82% Moriarty,R.M.etal.,J.Med.Chem.,1998,468 2)DIB(2.0eq.) I 2 (1.5eq.),AIBN benzene, reflux 92% 34 Rac I
35 To go further - More to know: Rest of DIB chemistry Iodosylbenzene (PhI) Koser's reagent (PhI(H)Ts) Togni's Reagent - Challenges: Chirality Mechanism understanding More reactivity still to be discovered 35
36 36
37 Thanks for your kind attention rganohypervalent iodine: Varvoglis, A., Synthesis 1984, Stang, P. J. and Zhdankin, V. V., Chem. Rev. 1996, Stang, P. J. and Zhdankin, V. V., Chem. Rev. 2002, Stang, P. J. and Zhdankin, V. V., Chem. Rev. 2008, Moriarty, R. M., J. rg. Chem. 2005,
Recent Developments in the Chemistry of Polyvalent Iodine Compounds
Recent Developments in the Chemistry of Polyvalent Iodine Compounds Jiang Zhongping 2005-9-23 Content I. Introduction II. Iodine(III) Compounds III. Iodine(V) Compounds IV. Conclusions Introduction Why
Hypervalent Iodine(III): Property and Reactivity. Penghao Chen g Dong Group Seminar October, 21 st, 2015
Hypervalent Iodine(III): Property and Reactivity Penghao Chen g Dong Group Seminar October, 21 st, 2015 Structure and Nomenclature Aryl λ 3 iodanes: L I L L : hypervalent bond with a pure 5p orbital Ar
Copper-catalyzed cleavage of benzyl ethers with diacetoxyiodobenzene and p-toluenesulfonamide
General Papers ARKIVC 2008 (xii) 103-108 Copper-catalyzed cleavage of benzyl ethers with diacetoxyiodobenzene and p-toluenesulfonamide Ling He a,b, Qin Wang a, Guo-Chuan Zhou b, Lei Guo b, and Xiao-Qi
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
The system PhIO/Ph 3 P as an efficient reagent for mild and direct coupling of alcohols with carboxylic acids
The system PhIO/Ph 3 P as an efficient reagent for mild and direct coupling of alcohols with carboxylic acids Maria A. Boulogeorgou, Virginia V. Triantakonstanti and John K. Gallos* Department of Chemistry,
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
Polyvalent Iodine in Synthesis (more than just Dess-Martin) Matthew M. Kreilein Wednesday, December 13 th, 2006
Polyvalent odine in Synthesis (more than just Dess-Martin) Matthew M. Kreilein Wednesday, December 13 th, 2006 General otes: + A LT older than though originally. + Cl 2 was the first reported polyvalent
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
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
Aziridine Carboxylates, Carboxamides and Lactones: New Methods for Their Preparation and Their Transformation into α- and β-amino Acid Derivatives
Molecules 2000, 5 293 Aziridine Carboxylates, Carboxamides and Lactones: ew Methods for Their Preparation and Their Transformation into α- and β-amino Acid Derivatives obert H. Dodd Institut de Chimie
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
Trivalent iodine chemistry A review of some compounds used as mild oxidising agents and their applications in modern organic synthesis
Trivalent iodine chemistry A review of some compounds used as mild oxidising agents and their applications in modern organic synthesis ntroduction n the last years, there has been considerable attention
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
General Papers ARKIVOC 2007 (xiii) 28-33
Hypervalent iodine oxidation of 1-phenyl-3-arylpyrazole-4- carboxaldehyde oximes: a facile and efficient synthesis of new 3,4-bis(1-phenyl-3-arylpyrazolyl)-1,2,5-oxadiazole--oxides m Prakash* and Kamaljeet
ChiralIonic Liquids. An Adolescent Technology. Jeremy Henle 1/24/12
ChiralIonic Liquids An Adolescent Technology Jeremy Henle 1/24/12 Strategies in Asymmetric Synthesis Chiral Induction Starting Materials Chiral Catalysts Chiral Solvents Enantioenriched Chiral Auxillaries
Tips for taking exams in 852
Comprehensive Tactical Methods in rganic Synthesis W. D. Wulff 1) Know the relative reactivity of carbonyl compounds Tips for taking exams in 852 Cl > > ' > > ' N2 eg: 'Mg Et ' 1equiv. 1equiv. ' ' Et 50%
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
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
Chromium Arene Complexes
Go through Reviews Chem. Reviews Chem. Soc. Reviews Book by Prof. A. J. Elias Chromium Arene Complexes Complexation of Cr(CO) 3 with ARENES Chromium arene complexes Metal complexation is appealing in organic
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
Discussion Addendum for: (Phenyl)[2-(trimethylsilyl)phenyl]iodonium Triflate. An Efficient and Mild Benzyne Precursor
![Discussion Addendum for: (Phenyl)[2-(trimethylsilyl)phenyl]iodonium Triflate. An Efficient and Mild Benzyne Precursor](/thumbs/82/85700948.jpg "Discussion Addendum for: (Phenyl)[2-(trimethylsilyl)phenyl]iodonium Triflate. An Efficient and Mild Benzyne Precursor")
DI:10.157/orgsyn.089.0098 Discussion Addendum for: (enyl)[-(trimethylsilyl)phenyl]iodonium Triflate. An Efficient and Mild Benzyne Precursor A. Cl Cl + Me 3 Cl Mg, I (cat.) HMPA 1 B. I(Ac) 1. TfH, CH Cl.
A Highly Efficient Organocatalyst for Direct Aldol Reactions of Ketones and Aldehydes
A ighly Efficient rganocatalyst for Direct Aldol Reactions of Ketones and Aldehydes Zhuo Tang, Zhi-ua Yang, Xiao-ua Chen, Lin-Feng Cun, Ai-Qiao Mi, Yao-Zhong Jiang, and Liu-Zhu Gong Contribution from the
Bowman Chem 345 Lecture Notes by Topic. Electrophilic Aromatic Substitution (EAS):
lectrophilic Aromatic Substitution (AS): Aromatic rings have a tendency to be unreactive due to their inherent stability. However, aromatic rings can react given the right incentives. ne way, they can
A Tandem Semipinacol Rearrangement/Alkylation of a-epoxy Alcohols: An Efficient and Stereoselective Approach to Multifunctional 1,3-Diols
A Tandem Semipinacol Rearrangement/Alkylation of a-epoxy Alcohols: An Efficient and Stereoselective Approach to Multifunctional 1,3-Diols B() 2 H H B() 2 H H Hu, X.-D.; Fan, C.-A.; Zhang, F.-M.; Tu, Y.
Total Syntheses of Minfiensine
Total Syntheses of Minfiensine Douany, A. B.; umphreys, P. G.; verman, L. E.*; Wrobelski, A. D., J. Am. Chem. Soc. 2008, ASAP. D: 10.1021/ja800163v Shen, L.; Zhang, M.; Wu, Y.; Qin, Y.*, Angew. Chem. nt.
Aroma'cs. Huckel rule 4n+2. Fully conjugated cyclic π system H N H N
Dearoma'za'on Nathan Brennan KU rganic Chemistry Problem Set C. Zhuo, and W. Zhang, Angew. Chem. Int. Ed. 2012, 51, 12662 S. P. Roche, and J. A. Porco, Angew. Chem. Int. Ed. 2011, 50, 4068 Huckel rule
Palladium-Catalyzed Oxygenation of Unactivated sp 3 C-H Bonds
Palladium-Catalyzed xygenation of Unactivated sp 3 C- Bonds Pd(Ac) 2 5 mol% PhI(Ac) 2 1.1 eq. Pd 2 Ac Desai, L. P.; ull, K. L.; Sanford *, M. S. University of Michigan J. Am. Chem. Soc. 2004, 126, ASAP
Organic Cumulative Exam April 26, 2018
rganic Cumulative Exam April, 0 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 indicate
MULTICOMPONENT REACTIONS AND ORGANOCATALYSIS: A SUITABLE COMBINATION FOR STEREOSELECTIVE SYNTHESIS OF HIGHLY SUBSTITUTED BENZAZEPINES
MULTICMPET REACTIS AD RGACATALYSIS: A SUITABLE CMBIATI FR STERESELECTIVE SYTHESIS F HIGHLY SUBSTITUTED BEZAZEPIES Martina Spallarossa Department of Chemistry and Industrial Chemistry, University of Genoa
ANSWER GUIDE APRIL/MAY 2006 EXAMINATIONS CHEMISTRY 249H
AWER GUIDE APRIL/MAY 2006 EXAMIATI CEMITRY 249 1. (a) PDC / C 2 2 (b) t-bume 2 i (1 equiv) / imidazole (1 equiv) i TBDM protection of the less sterically hindered alcohol (c) BuLi (1 equiv) then (d) 2
Reaction of Iodonium Ylides of 1,3-Dicarbonyl Compounds with HF Reagents
Molecules 2012, 17, 6625-6632; doi:10.3390/molecules17066625 Article PEN ACCESS molecules SSN 1420-3049 www.mdpi.com/journal/molecules Reaction of odonium Ylides of 1,3-Dicarbonyl Compounds with HF Reagents
Direct Catalytic Cross-Coupling of Organolithium
Literature report Direct Catalytic Cross-Coupling of Organolithium Compounds Reporter: Zhang-Pei Chen Checker: Mu-Wang Chen Date: 02/07/2013 Feringa, B.L.et al. Feringa, B. L. et al. Nature Chem. 2013,
Organocatalytic Umpolung via N- Heterocyclic Carbenes. Qinghe Liu Hu Group Meeting August 20 th 2015
rganocatalytic Umpolung via N- Heterocyclic Carbenes Qinghe Liu Hu Group Meeting August 20 th 2015 Contents Part 1: Introduction Part 2: N-Heterocyclic carbene-catalyzed umpolung: classical umpolung, conjugated
Strategies for Catalytic Asymmetric Electrophilic a Halogenation of Carbonyl Compounds
Strategies for Catalytic Asymmetric Electrophilic a alogenation of Carbonyl Compounds 1 2 Y Catalyst [X + ] 1 X! 2 Y intermann, L. ; Togni, A. Angew. Chem. Int. Ed. 2000, 39, 4359 4362 amashima, Y.; Sodeoka,
molecules ISSN
Molecules 2006, 11, 43-48 molecules ISS 1420-3049 http://www.mdpi.org Synthesis of Some ew 2-(3-Aryl-1-phenyl-4-pyrazolyl)- benzoxazoles Using Hypervalent Iodine Mediated Oxidative Cyclization of Schiff
Working with Hazardous Chemicals
A Publication of Reliable Methods for the Preparation of rganic Compounds Working with Hazardous Chemicals The procedures in rganic Syntheses are intended for use only by persons with proper training in
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
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
DAMIETTA UNIVERSITY. Energy Diagram of One-Step Exothermic Reaction
DAMIETTA UNIVERSITY CHEM-103: BASIC ORGANIC CHEMISTRY LECTURE 5 Dr Ali El-Agamey 1 Energy Diagram of One-Step Exothermic Reaction The vertical axis in this graph represents the potential energy. The transition
Keywords: amination ate complexes carbomagnesiation carbometalation Grignard reagents homocoupling magnesates magnesium compounds metalation
VII Abstracts 2010 p1 7.6.5.6 Aryl Grignard Reagents H. Yorimitsu Halogen magnesium exchange between aryl iodides or bromides and an isopropylmagnesium chloride lithium chloride complex or lithium trialkylmagnesates
Organic Cumulative Exam February 22, 2018
rganic Cumulative Exam February 22, 2018 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. early
Self-stable Electrophilic Reagents for Trifluoromethylthiolation. Reporter: Linrui Zhang Supervisor: Prof. Yong Huang Date:
Self-stable Electrophilic Reagents for Trifluoromethylthiolation Reporter: Linrui Zhang Supervisor: Prof. Yong Huang Date: 2017-12-25 Content Introduction Trifluoromethanesulfenates: Preparation and reactivity
Massachusetts Institute of Technology Organic Chemistry 5.512
Massachusetts Institute of Technology rganic Chemistry 5.512 Problem Set 6 Solutions Stereocontrolled Carbonyl Reduction and Aldol Reactions May 5, 2006 Lucy Kohnen ( The target compound was used as an
Suggested solutions for Chapter 41
s for Chapter 41 41 PBLEM 1 Explain how this synthesis of amino acids, starting with natural proline, works. Explain the stereoselectivity of each step after the first. C 2 C 2 3 CF 3 C 2 2 Pd 2 C 2 +
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.
TMSCl imidazole DMF. Ph Ph OTMS. Michael reaction. Michael reaction Ph R 3. epoxidation O R
eaction using diarylprolinol silyl ether derivatives as catalyst 1) C Et K C 3, ) MgBr, TF TMS hexane, 0 o C TBS p- C 6 4, T C Et 85%, 99% ee Angew. Chem., nt. Ed., 44, 41 (005). rg. Synth., 017, 94, 5.
Halogen Bond Applications in Organic Synthesis. Literature Seminar 2018/7/14 M1 Katsuya Maruyama
Halogen Bond Applications in Organic Synthesis Literature Seminar 2018/7/14 M1 Katsuya Maruyama 1 Contents 1. Introduction 2. Property of Halogen Bond 3. Application to Organic Synthesis 2 1. Introduction
2016 Pearson Education, Inc. Isolated and Conjugated Dienes
2016 Pearson Education, Inc. Isolated and Conjugated Dienes 2016 Pearson Education, Inc. Reactions of Isolated Dienes 2016 Pearson Education, Inc. The Mechanism Double Bonds can have Different Reactivities
Suggested solutions for Chapter 28
s for Chapter 28 28 PBLEM 1 ow would you make these four compounds? Give your disconnections, explain why you chose them and then give reagents for the. 2 2 Me S Exercises in basic one- group C X disconnections.
HYPERVALENT IODINE REAGENTS FOR TOSYL TRANSFER REACTIONS IN ORGANIC SYNTHESIS
HYPERVALENT IODINE REAGENTS FOR TOSYL TRANSFER REACTIONS IN ORGANIC SYNTHESIS A THESIS SUBMITTED TO THE FACULTY OF THE GRADUATE SCHOOL OF THE UNIVERSITY OF MINNESOTA BY SCOTT CLAY KLASEN IN PARTIAL FULFILLMENT
CHEMISTRY 252 Exam pts. Section 703 Grand Rapids 27 July 2006
ame PID CMISTRY 252 xam 1 100 pts. Section 70 Grand Rapids 27 July 2006 Make sure you have all 12 exam pages You will have 90 minutes to complete the 5 questions Please sign your name at the bottom of
trends in reactivity based on substitution of the starting iodoarene 5. 1) Pd(OAc) 2, CH 2 CN 2) HCl O Triethylamine
The eck Reaction Introduction The eck reaction is of great importance, as it results in a carbon- carbon bond through a metal catalyzed coupling reaction 1. The reaction involves an unsaturated halide,
Stereoselective reactions of enolates
1 Stereoselective reactions of enolates Chiral auxiliaries are frequently used to allow diastereoselective enolate reactions Possibly the most extensively studied are the Evan s oxazolidinones These are
Chapter 21. Phenols and Aryl Halides. Nucleophilic Aromatic Substitution. Ch. 21-1
Chapter 21 Phenols and Aryl alides Nucleophilic Aromatic Substitution Ch. 21-1 1. Structure and Nomenclature of Phenols Phenol 1-Naphthol (α-naphthol) 9-Phenanthrol Ch. 21-2 1A. Nomenclature of Phenols
Stereoselective reactions of enolates: auxiliaries
1 Stereoselective reactions of enolates: auxiliaries Chiral auxiliaries are frequently used to allow diastereoselective enolate reactions Possibly the most extensively studied are the Evan s oxazolidinones
Convergent Route to ent-kaurane Diterpenoids: Total Synthesis of Lungshengenin D and 1α6α- Diacetoxy-ent-kaura-9(11),16-dien- 12,15-dione
Convergent Route to ent-kaurane Diterpenoids: Total Synthesis of Lungshengenin D and 1α6α- Diacetoxy-ent-kaura-9(11),16-dien- 12,15-dione Xiangbo Zhao, Wu Li, Junjie Wang, and Dawei Ma* Shanghai Institute
Synthesis of Abyssomicin C. Marie-Caroline Cordonnier Litterature Review 23/01/2009
Synthesis of Abyssomicin C Marie-Caroline Cordonnier Litterature Review 23/01/2009 Isolation Isolated in 2004 from the actinomycete Verrucosispora strain collected from a sediment at a depth of 289m in
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
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,
CARBOXYLIC ACIDS and their Derivatives Nucleophilic Acyl substitution - Review the nomenclature for these compounds in your textbook
CARBXYLIC ACIDS and their Derivatives Nucleophilic Acyl substitution - Review the nomenclature for these compounds in your textbook R Z R Z R Z - the basicity of Z determines the relative stability of
CHEM 203. Final Exam December 15, 2010 ANSWERS. This a closed-notes, closed-book exam. You may use your set of molecular models
CEM 203 Final Exam December 15, 2010 Your name: ANSWERS This a closed-notes, closed-book exam You may use your set of molecular models This test contains 15 pages Time: 2h 30 min 1. / 16 2. / 15 3. / 24
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)
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
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
Recent applications of chiral binaphtholderived phosphoric acid in catalytic asymmetric reactions
Recent applications of chiral binaphtholderived phosphoric acid in catalytic asymmetric reactions 1. Seayad, J.; Seayad, A. M.; List, B. J. Am. Chem. Soc. 2006, ASAP. 2. Storer, R. L.; Carrera, D. E.;
Serendipitous synthesis of 1,4-benzothiazin derivatives using 2-[(2-aminophenyl)disulfanyl]aniline
![Serendipitous synthesis of 1,4-benzothiazin derivatives using 2-[(2-aminophenyl)disulfanyl]aniline](/thumbs/94/118068899.jpg "Serendipitous synthesis of 1,4-benzothiazin derivatives using 2-[(2-aminophenyl)disulfanyl]aniline")
erendipitous synthesis of 1,4-benzothiazin derivatives using 2-[(2-aminophenyl)disulfanyl]aniline Mohammad Reza Islami a *, Fouziyeh Mollazehi a, Alireza Badiei b, and assan heibani a a Department of Chemistry,
Direct Organocatalytic Enantioselective Mannich Reactions of Ketimines: An Approach to Optically Active Quaternary α-amino Acid Derivatives
Direct rganocatalytic Enantioselective Mannich eactions of Ketimines: An Approach to ptically Active Quaternary α-amino Acid Derivatives Wei Zhang, Steen Saaby, and Karl Anker Jorgensen The Danish ational
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
Nucleophilic Heterocyclic Carbene Catalysis. Nathan Werner Denmark Group Meeting September 22 th, 2009
Nucleophilic Heterocyclic Carbene Catalysis Nathan Werner Denmark Group Meeting September 22 th, 2009 Thiamine Thiamine Vitamin B 1 The first water-soluble vitamin described Is naturally synthesized by
Chapter 23 Phenols CH. 23. Nomenclature. The OH group takes precedence as the parent phenol.
CH. 23 Chapter 23 Phenols Nomenclature The OH group takes precedence as the parent phenol. Carboxyl and acyl groups take precedence over the OH group. The OH group is a strong electron-donating group through
Construction of Chiral Tetrahydro-β-Carbolines: Asymmetric Pictet Spengler Reaction of Indolyl Dihydropyridines
Literature Report V Construction of Chiral Tetrahydro-β-Carbolines: Asymmetric Pictet Spengler Reaction of Indolyl Dihydropyridines Reporter Checker Date : Xiao-Yong Zhai : Xin-Wei Wang : 2018-04-02 You,
CHEM 303 Organic Chemistry II Problem Set III Chapter 14 Answers
CHEM 303 rganic Chemistry II Problem Set III Chapter 14 Answers 1) Give the major products of each of the following reactions. If a mixture is expected, identify the major product. + H 3 CHC CHCH 3 H 2
SECTION 12. «POT-POURRI» in Organic Synthesis (2018)
SECTIN 12 «PT-PURRI» in rganic Synthesis (2018) 1 Total Synthesis of Erythromycin A via a Spiroketal ERYTRMYCIN A DESLNGCAMPS et al. Can. J. Chem. 1985, 63, 2810-2820. 2 Tetrahydropyran Derivative as Starting
3.7. Pyridinium Chloro Chromate (PCC):
xidation 3.7. Pyridinium hloro hromate (P): 97 l l r r 3 r l P is a very important oxidising reagent which will give controlled oxidation in the case of primary alcohol. It does not give over oxidation
Recent Advances of Alkyne Metathesis. Group Meeting Timothy Chang
Recent Advances of Alkyne Metathesis Group Meeting Timothy Chang 11-09-10 Fischer Carbyne and Schrock Alkylidyne Fischer Doublet LX type 4e Schrock Quartet X 3 type 6e -1-3 lone pair covalent p-back bonding
Supporting Information: Regioselective esterification of vicinal diols on monosaccharide derivatives via
Supporting Information: Regioselective esterification of vicinal diols on monosaccharide derivatives via Mitsunobu reactions. Guijun Wang,*Jean Rene Ella-Menye, Michael St. Martin, Hao Yang, Kristopher
Lecture 27 Organic Chemistry 1
CHEM 232 rganic Chemistry I at Chicago Lecture 27 rganic Chemistry 1 Professor Duncan Wardrop April 20, 2010 1 Self Test Question Nitrosonium (not nitronium) cations can be generated by treating sodium
Oxidative Dearomatization of phenols Hyung Min Chi Group Meeting Presentation
Oxidative Dearomatization of phenols 2011. 8. 23. Hyung Min Chi Group Meeting Presentation Outline Oxida&ve Dearoma&za&on Direc&onality / types Breaking aroma&city Common strategies used Applica&ons in
PROCESS FOR THE PREPARATION OF 5-CYANOPHTHALIDE AND INTERMEDIATES USEFUL THEREIN.
ABSTRACT: PRCESS FR THE PREPARATIN F 5-CYANPHTHALIDE AND INTERMEDIATES USEFUL THEREIN. Process for the preparation of 5-cyanophthalide is disclosed which comprises reacting a pharmaceutically acceptable
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
Literature Report IX. Cho, S. H. et al. Org. Lett. 2016, 18, Cho, S. H. et al. Angew. Chem. Int. Ed. 2017, 56,
Literature Report IX ynthesis of β-aminoboronates by Copper(I)- Catalyzed Addition of Diborylalkanes to Imines Reporter Checker Date : hubo Hu : Xiaoyong Zhai : 2017-9-1818 Cho,. H. et al. rg. Lett. 2016,
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
Nucleophilic Fluorination. Souvik Rakshit Burke group Literature Seminar July 13, 2013
Nucleophilic Fluorination Souvik Rakshit Burke group Literature Seminar July 13, 2013 Relevance 20% of pharmaceuticals contain fluorine 5-fluorouracil Antineoplastic agent, 1957 Lipitor (Atorvastatin)
Essential Organic Chemistry. Chapter 9
Essential Organic Chemistry Paula Yurkanis Bruice Chapter 9 Substitution and Elimination Reactions of Alkyl Halides 9.1 How Alkyl Halides React Substitution Reactions One group takes the place of another.
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
Catalytic Conjunctive Cross-Coupling enabled by Metal-Induced Metallate Rearrangement
Catalytic Conjunctive Cross-Coupling enabled by Metal-Induced Metallate earrangement L. Zhang, G. J. Lovinger, E. K. Edelstein, A. A. Szymaniak, M.. Chierchia, J.. Morken Science 2016, 351, 70-74. 1 Li
24.4: Acidity of Phenols. Phenols are more acidic than aliphatic alcohols. + Electron-withdrawing groups make an O
Chapter 24: Phenols. Alcohols contain an group bonded to an sp 3 -hybridized carbon. Phenols contain an group bonded to an sp 2 -hybridized carbon of a benzene ring 24.1: Nomenclature (please read) 24.2:
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,
Chemistry 3720 Old Exams. Practice Exams & Keys
Chemistry 3720 ld Exams Practice Exams & Keys 2015-17 Spring 2017 Page File 3 Spring 2017 Exam 1 10 Spring 2017 Exam 1 Key 16 Spring 2017 Exam 2 23 Spring 2017 Exam 2 Key 29 Spring 2017 Exam 3 36 Spring
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.
R.M. Williams. S Me O R H
C549.M. Williams xidations in ynthetic rganic Chemistry The Moffat and wern xidation eactions The classical Moffat oxidation (see: Pfitzner, K.E.; Moffatt, J.G., J. Am. Chem. oc. 1963, 85, 3027~3028),
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.
Lecture Notes Chem 51B S. King I. Conjugation
Lecture Notes Chem 51B S. King Chapter 16 Conjugation, Resonance, and Dienes I. Conjugation Conjugation occurs whenever p-orbitals can overlap on three or more adjacent atoms. Conjugated systems are more
Suggested solutions for Chapter 32
s for Chapter 32 32 PBLEM 1 Explain how the stereo- and regio- chemistry of these reactions are controlled. Why is the epoxidation only moderately diastereoselective, and why does the amine attack where
Chiral Diol Promoted Boronates Addi3on Reac3ons. Lu Yan Morken Group Boston College
Chiral Diol Promoted Boronates Addi3on Reac3ons Lu Yan Morken Group Boston College Main Idea R R B or R R B Ar * exchange B * * or B Ar R 1 R 1 R 2 R 1 R 2 Products not nucleophilic enough nucleophilic
Solution problem 22: Non-Benzoid Aromatic Sytems
Solution problem 22: on-enzoid Aromatic Sytems 22.1 & 22.2 Each double bond and each heteroatom (, ) with lone pairs donates 2 π- electrons as well as a negative charge. oron or a positive charge does
2.222 Practice Problems 2003
2.222 Practice Problems 2003 Set #1 1. Provide the missing starting compound(s), reagent/solvent, or product to correctly complete each of the following. Most people in the class have not done this type
Supporting Information
Supporting Information Wiley-VCH 2008 69451 Weinheim, Germany Supporting Information for Chiral Brönsted Acid Catalyzed Asymmetric Baeyer-Villiger Reaction of 3-Substituted Cyclobutanones Using Aqueous
Asymmetric Alklylation of Enolates
Asymmetric Alklylation of Enolates M with material from A G Meyers http://faculty.chemistry.harvard.edu/myers/pages/chem-215-handouts 745 rganic Synthesis Spring 2015 Asymmetric Alkylation - eed to control
Preparation, structure, and oxidative reactivity of (dichloroiodo)pyridines: recyclable hypervalent iodine reagents
The Free Internet J ournal for Organic Chemistry Paper Archive for Organic Chemistry Arkivoc 2018, part ii, 40-49 Preparation, structure, and oxidative reactivity of (dichloroiodo)pyridines: recyclable