A Perspective on Professor Scott Eric Denmark: The Man, The Myth, The Chemist O
|
|
|
- Eugenia Philomena Thomas
- 7 years ago
- Views:
Transcription
1 A Perspective on Professor Scott Eric Denmark: The Man, The Myth, The Chemist Si 3 2 C 2 S P (C 2 ) 5 2 n-c 5 9 ussell C. Smith Stoltz/eisman Group eting January 24, 2011 Si M
2 From umble Beginnings Born in Lynbrook, ew York on 17 June 1953 btained an S. B. degree from M.I.T. in 1975 Conducted research with both ichard. olm (ferredoxin analogs) and Daniel S. Kemp (functionalized cyclophanes). eceived D. Sc. Tech degree in 1980 Prof. Dr. Albert Eschenmoser ( n the Stereochemistry of the S eaction ) Independent career as assistant professor at the University of Illinois at Urbana-Champaign Associate Professor 1987 Full Professor 1991 eynold C. Fuson Professor of Chemistry. steps S 2 S B B J. rg. Chem. 1981, 46, 3144
3 To A Thriving Career In rganic Chemistry: utline Silicon-Directed azarov Cyclization thexyl 2 Si Si 3 Bn BF 3 Et 2 C 6 5 Et, 125 C thexyl 2 Si Inter/Intramolecular [42]/[32] Cycloaddition of itro lefins 2 C 1. SnCl 4 C 2 Cl 2, -78 C 2. toluene, 80 C Lewis-Base Activation of Lewis Acids Enantioselective Carbon- Carbon Bond Formation C SiCl 4 Et TBS Bn 2 Si C P C 2 2 Bn 2 Si C 2 Et
4 To A Thriving Career In rganic Chemistry: utline Silicon-Directed azarov Cyclization thexyl 2 Si Si 3 Bn BF 3 Et 2 C 6 5 Et, 125 C thexyl 2 Si Inter/Intramolecular [42]/[32] Cycloaddition of itro lefins 2 C 1. SnCl 4 C 2 Cl 2, -78 C 2. toluene, 80 C Lewis-Base Activation of Lewis Acids Enantioselective Carbon- Carbon Bond Formation C SiCl 4 Et TBS Bn 2 Si C P C 2 2 Bn 2 Si C 2 Et
5 azarov Cyclization Background amed after the ussian chemist I.. azarov ( ), 2 gs 4, 2 S 4 Proved later that the cyclization proceeds through a divinyl ketone 3 P 4, C 2 90 C Incorporation of nucleophile gave further insight into mechanism 2 S 4 Ac 2, C a rg. eact. 1994, 45, 1-158
6 azarov Cyclization chanism * * * * * Promoted by thermal or photochemical initiation 254 nm, C 6 6 Ac, 3 P 4 50 C rg. eact. 1994, 45, 1-158
7 azarov Cyclization chanism * * * * * emote substituents can cause changes in the torquoselectivity of the cyclization clockwise counterclockwise rg. eact. 1994, 45, 1-158
8 Silicon-Directed azarov Cyclization C 3 Si MgBr 1. TF, -20 C 2. 4 Cl Si 3 i 2 Et 2, 0 C Si 3 FeCl 3 (1.05 equiv) Si 3 C 2 Cl 2 55%, 100% cis 84%, 100% cis 74%, 85/15 cis/trans 95%, 59/41 cis/trans Use of Si functionality directs collapse of cation J. Am. Chem. Soc. 1982, 104, 6242.
9 SDC Effect of Allylic Position Larger substituents promote increased levels of torquoselectivity (presence of vinyl silane) FeCl 3 Si 3 C 2 Cl 2 (C,T) (C,C) (C,T) (C,C) yield, % C 2 =C t-bu C Tetrahedron 1986, 48, 2821
10 SDC Effect of Silicon Functionality FeCl 3 Si 3 C 2 Cl 2 (C,T) (C,C) (C,T) (C,C) yield, % 2 Si For Si 3 = 54/46 2 Si 3 Si for Si(i-Pr) 3 = 79/21 I-Pr 3 Si Tetrahedron 1986, 48, 2821
11 Formation of Enantioenriched Carbocycles Via SDC Si 3 FeCl 3 Br Br Br Br 2 C 2 Cl 2, -50 C 58%, 88% ee CCl 4 70% yield anti Si 3 M n Si 3 Si 3 M n Si 3 M n syn J. rg. Chem. 1990, 55, 5544
12 Total Synthesis of Silphinene: Application of SDC Bn = Si 2 thexyl Mn 2 C 2 Cl 2, 20 C 98% yield C Bn MgBr 3 Si TF, -30 C 80% yield Si 3 Bn Si 3 Mn 2 C 2 Cl 2, -40 C Bn BF 3 Et 2 C 6 5 Et, 125 C silphinene Presence of silicon functionality directs formation of cyclopentenone Tetrahedron 1997, 53, 2103
13 To A Thriving Career In rganic Chemistry: utline Silicon-Directed azarov Cyclization Inter/Intramolecular [42]/[32] Cycloaddition of itro lefins 2 thexyl 2 Si C Si 3 Bn BF 3 Et 2 C 6 5 Et, 125 C 1. SnCl 4 C 2 Cl 2, -78 C 2. toluene, 80 C Lewis-Base Activation of Lewis Acids Enantioselective Carbon- Carbon Bond Formation thexyl 2 Si C SiCl 4 Et TBS Bn 2 Si C P C 2 2 Bn 2 Si C 2 Et
14 Intramolecular Cycloaddition of itrosoalkenes eactivity of itrosoalkenes ' Cl base - ' uc ' uc Intermediate nitrosoalkene can act as 2π or 4π cycloaddition component 2 t-busi Cl CsF (3.0 equiv) C 3 C, 20 C 75/25 E/Z 70% yield 13% isomer 50/50 E/Z 32% yield (3.4/1 ratio of isomers J. rg. Chem. 1984, 49, 4714
15 itroolefins as 4π Components in Cycloadditions - SnCl 4 toluene, -29 C - 80% yield > 98/2 trans/cis J. Am. Chem. Soc. 1986, 108, 1306 itro groups serve as useful functionality for further elaboration - SnCl 4 C 2 Cl 2, -70 C - Kt-amyl -70 C Cl C 2 - SnCl 4 C 2 Cl 2, -70 C - C 2 2 C elv. Chim. Acta. 1986, 69, 1971
16 - Intramolecular [32] Cycloaddition Z Z' 1. SnCl 4 toluene, -78 C 2. toluene, 70 C Z' Z Z Z time, h [42] time, h [32] ds yield, % C 2 Et 7 0 >100:1 72 C 2 Et : Z Z' 1. SnCl 4 C 2 Cl 2, -78 C 2. toluene, 80 C Z' Z Z Z time, min [42] time, h [32] ds yield, % C 2 Et 25 7 >100:1 93 C 2 Et :1 90 J. Am. Chem. Soc. 1990, 112, 311
17 Tandem Double Intramolecular [42]/[32] Cycloaddition Fused/bridged C(6) - 1. SnCl 4 toluene, -78 C C 2 2. ac 3 toluene, 80 C 82% yield 2 C a-i 2 (160 psi), rt 71% yield Fused/bridged C(5) - 1. SnCl 4 C 2 Cl 2, -78 C 2. ac 3 toluene, 100 C 79% yield 1. a-i 2 (160 psi), rt 2. Ac 2, py 82% yield Ac Ac Cycloaddition can be rendered diastereoselective by presence of chiral auxiliary rg. Lett. 2001, 3, 2907
18 Total Synthesis of ()-Crotanecine 2 C 2 i-pr Al 2 i-pr 2 C G* L-selectride Si 2 toluene, -14 C 73% yield Si 2 C 2 Cl, -78 C 91% yield i-pr 2 C G* Si 2 a-i 200 psi 2 Et 58% yield Si % ee 1. C()3 Ts 2. 2 S 2 Cl, Et 3 3. Ac, KBr AC, aac 4. 90% TFA 3 S B 3, TF 3 S B 3 Et 3, C rosmarinecine (intra) hastanecine (inter) macronecine (inter) J. Am. Chem. Soc. 1997, 119, 125
19 1-Azafenestranes: Planarization of sp 3 Carbon Center 2 Cu(C)ZnI 2 Se t-bu then SeBr Al 3 C 2 Cl 2, -78 C t-bu - t-bu a-i, 2 10% 2 in EtAc P 3, DIAD then B 3 TF -78 C to rt B 3 B 3 BF 3 BF 3 Et C(8)-C(1)-C(2) C(1)-C(5) ray quality
20 To A Thriving Career In rganic Chemistry: utline Silicon-Directed azarov Cyclization Inter/Intramolecular [42]/[32] Cycloaddition of itro lefins thexyl 2 Si 2 C Si 3 Bn BF 3 Et 2 C 6 5 Et, 125 C 1. SnCl 4 C 2 Cl 2, -78 C 2. toluene, 80 C Lewis-Base Activation of Lewis Acids Enantioselective Carbon- Carbon Bond Formation thexyl 2 Si C SiCl 4 Et TBS Bn 2 Si C P C 2 2 Bn 2 Si C 2 Et
21 Lewis-Base Activation of Lewis Acids P 3 B 3 P B stable Adduct mp = 100 C stable in 2 Preparative Examples I dioxolane t 1/2 = 80 min Li I dioxolane 4 eq. MPA t 1/2 = < 1 min Tf Tf Et ZnEt 2 Ti(i-Pr) 4 (1.2 equiv) 23 C, 12 h C ZnEt 2 Ti(i-Pr) 4 (1.2 equiv) -20 C, 1.5 h Et 98% ee EVIEW: Angew. Chem Int. Ed. 2008,47, 1560
22 L Lewis-Base Activation of Lewis Acids Principles Gutmann Analysis L L D A e.g. B 3 Lewis Base Lewis Acid increased negative charge! L! L D L A!! increased positive charge L L D L A cationic Lewis Acid L D L L A Lewis Base Lewis Acid! L! L D L! A! L L D A L cationic Lewis Acid e.g. SiCl 4 increased negative charge increased positive charge EVIEW: Angew. Chem Int. Ed. 2008,47, 1560
23 Lewis-Base Activation of Lewis Acids Principles ybridization of Silicon EVIEW: Angew. Chem Int. Ed. 2008,47, 1560
24 Aldol eaction of Silicon-Substituted Enolates Uncatalyzed SiCl 3 1. C 2 Cl 2, 0 C 2. sat. aq ac 3 Cy t-bu (E)-cinnamyl yield, % SiCl 3 1. P 0.1 equiv C 2 Cl 2, -78 C = (E)-cinammyl 2. sat. aq. ac 3, anti/syn 65/1, 93% ee (E)-cinnamyl, anti/syn >99/1, 88% ee J. Am. Chem. Soc. 1996, 118, 7404
25 Addition to Ketones Silyl Ketene Acetals SiCl 3 ' t-bu Bu Bu 1. C 2 Cl 2, 0 C 2. sat. aq ac 3 t-bu ' Et F 3 C 95%, 83% ee 91%, 76% ee 94%, 68% ee 97%, 49% ee 86%, 8% ee 91%, 32% ee 90%, 80% ee 94%, 35% ee J. Am. Chem. Soc. 2002, 124, 4234
26 Vinylogous Aldol 1 4 TBS 5 P 2 SiCl 4, C 2 Cl 2, -78 C 3 C Et Et 89%, >99:1!/", 98% ee 93%, >99:1!/", 99% ee 73%, >99:1!/", 95% ee t-bu t-bu 92%, >99:1!/", 89% ee, 98% de 71%, >99:1!/", 82% ee, 98% de chiral phosphoramide TBS SiCl 4, C 2 Cl 2, -78 C 92% yield, >99:1!/", 74% ee J. Am. Chem. Soc. 2003, 125, 2800
27 Formation of Quaternary Centers Silyl Ketene Imines C 1 2 C TBS 5 mol% chiral phosphormaide SiCl 4 C 2 Cl 2, -78 C 1 2 C C Et C C Et 87%, 95/5 dr, 97% ee F 3 C 73%, 97/3 dr, 99% ee 74%, 87/13 dr, 89% ee C C TBS 5 mol% chiral phosphormaide SiCl 4 C 2 Cl 2, -78 C C dr ee, % yield, % 4-CF 3 >99: >99: naphthyl >99: furyl 99: J. Am. Chem. Soc. 2007, 129, 14864
28 -Silyl xyketene Imines Aldol Surrogates cross-benzoin Si C 1 Pg 2 cat C Pg 1 2 glycolate-aldol 3 Pg 1 2
29 -Silyl xyketene Imines Aldol Surrogates C t-bu KMDS (1.2 equiv) i-pr 3 SiCl (1.1 equiv) TF, -78 C (i-pr) 3 Si C t-bu where =, Er, i-bu, Bn, allyl (i-pr) 3 Si C t-bu P SiCl 4, i-pr 2 Et C 2 Cl 2, -78 C C 2 2 t-bu C Aryl t-bu C t-bu C t-bu C 84%, 96:4 dr, 99% ee 93%, 99:1 dr, 99% ee 90%, 99:1 dr, 99% ee t-bu C C 2 91%, 98:2 dr, 97% ee t-bu C 93%, 99:1 dr, 97% ee t-bu C 91%, 99:1 dr, 99% ee at. Chem. 2010, 2, 937
30 Total Synthesis of K-397 Synthesis of Polyol Fragment Bn 2 Si Bn 2 Si 1. ed-al 2. DMS (CCl)2 Et 3 C 2 Et C KMDS Bn 2 Si Bn 2 Si C TBS Et C 2 Et SiCl 4 P C %, 96% ee 74%, 19/1 dr 1. TMSTf, DIPEA 1. -Cl i-prmgcl 2. MgBr Bn 2 Si C() 2. SiCl 4, g(ac) 2 3. PMB C P Bn 2 Si PMB 1. ab 4 2. C() 2 CSA Bn 2 Si PMB
31 Total Synthesis of K-397 Synthesis of Polyene Fragment Bn 2 Si Si 2 I TP 1. a 2. Pd 2 (dba) 3 CCl 3 Bn 2 Si TP 77%, 3/1 dr I C 2 Et TP Pd(dba) 2 Et 79%, 5/1 dr 1. Ts, I 2 2. PBr 3, py P(Et) 3 3. P(Et) 3 Et 93% 8 of 10 stereocenters were generated by substrate control
32 Eli Lilly esearch Grantee, 1983 Beckman Endowment esearch Award, 1983 University of Illinois Center for Advanced Study, Beckman Fellow, Spring 1985 A. P. Sloan Foundation Fellow, SF Presidential Young Investigator Award, Procter and Gamble University Exploratory esearch Program Award, University Scholar, University of Illinois, School of Chemical Sciences Teaching Award, University of Illinois, 1986 Stuart armaceuticals Award in Chemistry, ICI Americas, 1987 A. C. Cope Scholar Award, American Chemical Society, 1989 Awards/ecognition Fellow, American Association for the Advancement of Science, 1990 eynold C. Fuson Professor of Chemistry, 1991 Pedler dal (oyal Society of Chemistry), ACS Award for Creative Work in Synthetic rganic Chemistry, 2003 Yamada-Koga Prize (Japan esearch Foundation for ptically Active Compounds), 2006 Fellow, oyal Society of Chemistry (FSC), 2006 Prelog dal (ET-Zürich, Switzerland), 2007 obert obinson dal and Lectureship (oyal Society of Chemistry), C. Brown Award for Creative esearch in Synthetic thods (ACS), 2009 Fellow, American Chemical Society, 2009 (inaugural year)
33
David W. C. MacMillan Career-in-Review. Sujun Wei BreslowGroup Columbia University September 28, 2007
David W. C. MacMillan Career-in-Review Sujun Wei BreslowGroup Columbia University September 28, 2007 Biography 1968: Born in Bellshill, Scotland 1987-1991: B.S. at the University of Glasgow, Scotland 1991-1996:.D.
Allyl Metals. oxidative addition. transmet. + M(n) η 1 -allyl. n = 0, 1. base. X η 3 -allyl. Nuc. insertion. insertion. M(n+2)X MgX + MX2 MX 2
Allyl tals Virtually all transition metals can form η 3 -allyl complexes, but few are synthetically useful. Pd is most widely studied and has broad utility. Allyl complexes of h, Ir, u and Mo are becoming
FIVE-MEMBERED RING FORMATION 138. 5 Membered Rings. Intramolecular S N 2 Reaction
5 mbered ings FIVE-MEMBEED IG FMATI 138 C 2 C 2 PGF 2α PGE 2 irsutene Modhephane Isocumene 1. Intramolecular S 2 eactions 2. Intramolecular Aldol Condensation and Michael Addition 3. Intramolecular Wittig
Wittig Reaction - Phosphorous Ylides
Wittig eaction - osphorous Ylides 3 P CC 3 3 C ylide tereoselectivity increases as the size of increases cis-olefin is derived from non-stabilized ylides Mechanism: Irreversible [22] cycloaddition P 3
Cleavage of Cyclobutanols and Cyclobutanones
Literature Report VII Transition Metal-Catalyzed Enantioselective C-C C Bond Cleavage of Cyclobutanols and Cyclobutanones Huang, W.-X. checker: Yu, C.-B. 2014-04-2904 29 1 Contents 1. Background Information
Properties of Silicon
Properties of Silicon afensteiner Si vs. C - Si is less electronegative than C - More facile nucleophilic addition at Si center Average BDE (kcal/mol) C C C Si Si Si C F Si F 83 76 53 116 135 C Si C Si
Stille, Suzuki, and Sonogashira Couplings Cross-Coupling reactions: catalyst R-X + R'-M
Stille, Suzuki, and Sonogashira Couplings Cross-Coupling reactions: catalyst -X '-M -' M-X, ' are usually sp 2 hybridized X= (best), Tf, r, Cl M=Sn,, Zn, Zr, n Catalyst= Pd, sometimes Ni Example: Pd(0)
- Alder Endo Rule: In order to maximize secondary orbital interactions, the endo TS is favored in the D-A rxn. Tetrahedron 1983, 39, 2095 X X.
6-MEMEED IG FMTI 150 Six mbered ings 1. Diels-lder eaction 2. o-quinodimethanes 3. Intramolecular ene reaction 4. Cation olefin cyclizations 5. obinson annulation Diels-lder eaction CIEE 1984, 23, 876;
Kurs: Metallorganische Reagenzien. Cericammoniumnitrate (CAN)
Kurs: Metallorganische eagenzien Cericammoniumnitrate (CAN) by Laura Munoz Senovilla and Arthur Fedoseev. CAN as one-electronelectron oxidant CAN as one-electron electron oxidant Based on: Salt of high-valent
SYNTHETIC STUDIES ON TULEARIN MACROLIDES. M.Montserrat Martínez, Luis A. Sarandeses, José Pérez Sestelo
SYNTHETIC STUDIES N TULEARIN MACRLIDES M.Montserrat Martínez, Luis A. Sarandeses, José Pérez Sestelo Departamento de Química Fundamental, Universidade da Coruña, E-15071 A Coruña, Spain E-mail: mmartinezc@udc.es
Prof. Dr. Burkhard König, Institut für Organische Chemie, Uni Regensburg 1. Enolate Chemistry
Prof. Dr. Burkhard König, Institut für rganische Chemie, Uni Regensburg 1 1. Some Basics Enolate Chemistry In most cases the equilibrium lies almost completely on the side of the ketone. The ketone tautomer
Aldehydes can react with alcohols to form hemiacetals. 340 14. Nucleophilic substitution at C=O with loss of carbonyl oxygen
340 14. Nucleophilic substitution at C= with loss of carbonyl oxygen Ph In Chapter 13 we saw this way of making a reaction go faster by raising the energy of the starting material. We also saw that the
Stegane natural products
Me Me Me Indroduction: Steganone -Isolation from Steganotaenia araliacea in 1972 from Kupchan -Belong to the category of lignans Biological Properties: -Significant activity in vivo against P-388 leukemia
ammonium salt (acidic)
Chem 360 Jasperse Ch. 19 otes. Amines 1 eactions of Amines 1. eaction as a proton base (Section 19-5 and 19-6) amine base -X (proton acid) a X ammonium salt (acidic) Mechanism: equired (protonation) everse
Conjugation is broken completely by the introduction of saturated (sp3) carbon:
Chapter 16 Conjugation, resonance, and dienes Conjugation relies on the partial overlap of p-orbitals on adjacent double or triple bonds. A common conjugated system involves 1,3-dienes, such as 1,3-butadiene.
Mitsunobu Reaction (1934-2003)
Mitsunobu eaction (1934-2003) utline General Information: Who discovered this? What is the basic reaction? The Mechanism: What exactly happens and how? Applications: i) Variations of the method- where
CHEM 211 CHAPTER 16 - Homework
CHEM 211 CHAPTER 16 - Homework SHORT ANSWER Consider the Friedel-Crafts alkylation reaction below to answer the following question(s): 1. Refer to the reaction above. Draw the structure of the electrophilic
Guide to Solving Sophomore Organic Synthesis Problems
Paul Bracher Chem 30 Synthesis eview Guide to Solving Sophomore rganic Synthesis Problems Disclaimer mission of a topic on this handout does not preclude that material from appearing on the final exam.
A REVIEW OF GENERAL CHEMISTRY: ELECTRONS, BONDS AND MOLECULAR PROPERTIES
A REVIEW OF GENERAL CEMISTRY: ELECTRONS, BONDS AND MOLECULAR PROPERTIES A STUDENT SOULD BE ABLE TO: 1. Draw Lewis (electron dot and line) structural formulas for simple compounds and ions from molecular
Metal catalysed asymmetric epoxidation of olefins
Metal catalysed asymmetric epoxidation of olefins First report: chiral molybdenum peroxo complexes squalene Mo 2 (acac) 2, di-isopropyl tartrate 14% ee S tsuka et al, Tetrahedron Lett. 1979, 3017 Iron
pka's of Inorganic and Oxo-Acids
's of Inorganic and xo-acids ubstrate 2 3 2 Br Cl F Cl Cl 4 C 3 C 2 3 2 4 3 P 4 3 2 2 Cr 4 C 3 3 3 4 Cl B() 3 IRGAIC ACID Table.1 11/4/05 1:43 PM 2 15.7-1.7 7.00-9.00-8.0 3.17 7.5-10 9.4 4.72 4.00-14 11.6
Benzene Benzene is best represented as a resonance hybrid:
Electrophilic Aromatic Substitution (EAS) is a substitution reaction usually involving the benzene ring; more specifically it is a reaction in which the hydrogen atom of an aromatic ring is replaced as
5.5 Vicinal Proton-Proton Coupling 3 J HH
5.5 Vicinal Proton-Proton Coupling 3 J Copyright ans J. Reich 21 All Rights Reserved University of Wisconsin The single most useful - coupling relationship is that between vicinal protons. The size of
Metal Catalyzed Redox Reactions
tal Catalyzed edox eactions athan Jui MacMillan Group eting January 27, 2010 tal Catalyzed edox eactions! Many metal-catalyzed reactions involve redox processes Cross-Coupling Chemistry eduction Chemistry
Asymmetric Epoxidation of Pentadienols
10 Asymmetric Epoxidation of Pentadienols Asymmetric Epoxidation of Pentadienols Reinhard Brçckner, University of Freiburg, Germany Background The asymmetric epoxidation of allylic alcohols or Sharpless
Lewis-Base Catalysis. MacMillan Lab. Group Meeting Anthony Mastracchio November 5 2008
ewis-base Catalysis MacMillan ab. Group eting Anthony Mastracchio ovember 5 2008 ewis Base Catalysis resentation utline Introduction Definitions and basic concepts of ewis base Catalysis n π* interactions
Short Peptide Synthesis
Short Peptide Synthesis Keith ó Proinsias 8 th February 2010 Introduction Amide bond and basic amide synthesis Solution phase peptide synthesis Protecting groups required for peptide synthesis Coupling
Carboxylic Acid Derivatives and Nitriles
Carboxylic Acid Derivatives and itriles Carboxylic Acid Derivatives: There are really only four things to worry about under this heading; acid chlorides, anhydrides, esters and amides. We ll start with
Name Key 215 F12-Exam No. 2 Page 2
ame Key 15 F1-Exam o. Page. (9 points) For each of the following sets of molecules, rank the molecules in order of to least acidic. ompare the underlined s for each set. (a) (b) (c). (11 points) Draw in
1. What is the hybridization of the indicated atom in the following molecule?
Practice Final Exam, Chemistry 2210, rganic Chem I 1. What is the hybridization of the indicated atom in the following molecule? A. sp 3 B. sp 2 C. sp D. not hybridized 2. Name the functional groups in
Properties of a molecule. Absolute configuration, Cahn-Ingold Prelog. Planar, axial, topological chirality and chirality at atoms other than carbon
Key stereochemical terminology Stereochemical terminology in organic chemistry can refer to structure of a molecule or to properties of a physical sample of the molecule. It is very important to recognize
California State Polytechnic University, Pomona. Exam Points 1. Nomenclature (1) 30
Chem 316 Final Exam Winter, 2008 Beauchamp ame: Topic Total Points Exam Points 1. omenclature (1) 30 Credit 2. Explanation of elative eactivities of Aromatic 20 Compounds or Carbonyl Compounds 3. eactions
Chapter 6. Alkenes: Structure and Stability
hapter 6. Alkenes: Structure and Stability Steric Acid (saturated fatty acid) Linoleic Acid (unsaturated fatty acid) Degrees of unsaturation saturated hydrocarbon n 2n2 cycloalkane (1 ring) n 2n alkene
Aminohydroxylation of Olefins: Development and Applications
Aminohydroxylation of lefins: Development and Applications by Manish awat Michigan State University Jan 17 th, 2001 utline 1. Aminohydroxylation of olefins a. t-butyl amine as source b. Chloramine-T as
FREE RADICAL REACTIONS A STUDENT WHO HAS MASTERED THE MATERIAL IN THIS SECTION SHOULD BE ABLE TO:
FREE RADICAL REACTIONS A STUDENT WO AS MASTERED TE MATERIAL IN TIS SECTION SOULD BE ABLE TO: 1. Define, recognize, and give examples of: homolytic cleavage (homolysis), heterolytic cleavage, free radical,
methyl RX example primary RX example secondary RX example secondary RX example tertiary RX example
ucleophilic Substitution & Elimination hemistry 1 eginning patterns to knowfor S and E eactions - horizontal and vertical templates for practice Example 1 - two possible perspectives (deuterium and tritium
Recent Developments in Homogeneous Gold Catalysis
ecent Developments in omogeneous Gold Catalysis David A. Nagib MacMillan Group Literature Meeting 03.17.2010 elativistic ffects in Gold Catalysis elativistic effects phenomenon resulting from the need
ALKENES AND ALKYNES REACTIONS
A STUDENT SHULD BE ABLE T: ALKENES AND ALKYNES REACTINS 1. Given the starting materials and reaction conditions, predict the products of the following reactions of alkenes and alkynes. Regioselective Markovnikov
Double Bonds. Hydration Rxns. Hydrogenation Rxns. Halogenation. Formation of epoxides. Syn addition of 2 OH. Ozonolysis
Double Bonds What do we do with double bonds? We do addition reactions. In an addition reaction, something is added to both carbons involved in a double bond (or not involved in the double bond, in the
ACID and BASES - a Summary
AID and BASES - a Summary Stefan Svensson 2004 Brönsted-Lowry : Acids donate protons Lewis -acid : Electron pair acceptor Bases accept protons Lewis-base: Electron pair donator. Acetic acid ättiksyra 3
Chapter 6 An Overview of Organic Reactions
John E. McMurry www.cengage.com/chemistry/mcmurry Chapter 6 An Overview of Organic Reactions Why this chapter? To understand organic and/or biochemistry, it is necessary to know: -What occurs -Why and
ch9 and 10 practice test
1. Which of the following covalent bonds is the most polar (highest percent ionic character)? A. Al I B. Si I C. Al Cl D. Si Cl E. Si P 2. What is the hybridization of the central atom in ClO 3? A. sp
pk a Values for Selected Compounds
Appendix A pk a Values for Selected ompounds ompound pk a ompound pk a I 10 Br 9 2 S 4 9 + 3 3 7.3 3 S 3 7 Br 4.0 4.2 3 4.3 2 N l 7 [( 3 ) 2 ] + 3.8 [ 3 2 ] + 2.5 3 + 1.7 3 S 3 1.2 + 3 N2 0.0 F 3 0.2 l
ALKENES AND ALKYNES REACTIONS A STUDENT WHO HAS MASTERED THE MATERIAL IN THIS SECTION SHOULD BE ABLE TO:
ALKENES AND ALKYNES REACTINS A STUDENT W AS MASTERED TE MATERIAL IN TIS SECTIN SULD BE ABLE T: 1. Given the starting materials and reaction conditions, predict the products of the following reactions of
Chapter 3: Protecting Groups
I. Protecting Groups of Hydroxyl Groups Chapter 3: Protecting Groups Consider the stability and effect of anomeric group! Consider the solubility of starting material (the choice of solvent)! Consider
Reminder: These notes are meant to supplement, not replace, the textbook and lab manual. Electrophilic Aromatic Substitution notes
Reminder: These notes are meant to supplement, not replace, the textbook and lab manual. Electrophilic Aromatic Substitution notes History and Application: The rate of a reaction directly impacts the commercial
EXPERIMENT 5: DIPEPTIDE RESEARCH PROJECT
EXPERIMENT 5: DIPEPTIDE RESEARCH PROJECT Pre-Lab Questions: None. 64 I. Background Information DIPEPTIDE RESEARCH PROJECT Methods developed by organic chemists for the synthesis of biopolymers have had
Self Assessment_Ochem I
UTID: 2013 Objective Test Section Identify the choice that best completes the statement or answers the question. There is only one correct answer; please carefully bubble your choice on the scantron sheet.
Supplementary Information. Primary amino acid lithium salt as a catalyst for asymmetric Michael addition of isobutyraldehyde with β-nitroalkenes.
This journal is (c) The Royal Society of Chemistry 8 Supplementary Information Primary amino acid lithium salt as a catalyst for asymmetric Michael addition of isobutyraldehyde with β-nitroalkenes. Atsushi
Molecule Projections
Key Definitions ü Stereochemistry refers to the chemistry in 3 dimensions (greek stereos = solid). This science was created by Pasteur (1860), van Hoff et LeBel (1874). ü Stereisomers are isomeric molecules
Chapter 2 Polar Covalent Bonds: Acids and Bases
John E. McMurry www.cengage.com/chemistry/mcmurry Chapter 2 Polar Covalent Bonds: Acids and Bases Modified by Dr. Daniela R. Radu Why This Chapter? Description of basic ways chemists account for chemical
Study of the Thermal Behavior of Azidohetarenes with Differential Scanning Calorimetry
Fourth International Electronic Conference on Synthetic Organic Chemistry (ECSOC-4), www.mdpi.org/ecsoc-4.htm, September 1-30, 2000 [A0066] Study of the Thermal Behavior of Azidohetarenes with Differential
Hamari Chemicals, Ltd.
amari Chemicals, Ltd. Technology for Life 1 Agenda What amari can offer your company amari s Technology The amari Advantage Core Technology unnatural amino acids and peptides; reduction; chiral technologies;
Organometallics Study Seminar Chapter 13: Metal-Ligand Multiple Bonds
Organometallics Study Seminar Chapter 13: Metal-Ligand Multiple Bonds Contents 1. Carbene Complexes 2. Silylene Complexes 3. Metal-Heteroatom Multiple Bonds 1. Carbene Complexes 1.1 Classes of Carbene
Electrophilic Addition Reactions
Electrophilic Addition Reactions Electrophilic addition reactions are an important class of reactions that allow the interconversion of C=C and C C into a range of important functional groups. Conceptually,
SOME TOUGH COLLEGE PROBLEMS! .. : 4. How many electrons should be shown in the Lewis dot structure for carbon monoxide? N O O
SME TUGH CLLEGE PRBLEMS! LEWIS DT STRUCTURES 1. An acceptable Lewis dot structure for 2 is (A) (B) (C) 2. Which molecule contains one unshared pair of valence electrons? (A) H 2 (B) H 3 (C) CH 4 acl 3.
Studying an Organic Reaction. How do we know if a reaction can occur? And if a reaction can occur what do we know about the reaction?
Studying an Organic Reaction How do we know if a reaction can occur? And if a reaction can occur what do we know about the reaction? Information we want to know: How much heat is generated? How fast is
Microreactors and Microfluidic Cells in Organic Synthesis. MacMillan Group Meeting December 12, 2007 Joe Carpenter
Microreactors and Microfluidic Cells in rganic Synthesis MacMillan Group eting December 12, 2007 Joe Carpenter Microreactors and Microfluidic Cells in rganic Synthesis Presentation utline n Introduction
2. Couple the two protected amino acids.
General Considerations The Strategy of Peptide Synthesis Making peptide bonds between amino acids is not difficult. The challenge is connecting amino acids in the correct sequence. andom peptide bond formation
Nucleophilic Substitution and Elimination
Nucleophilic Substitution and Elimination What does the term "nucleophilic substitution" imply? A nucleophile is an the electron rich species that will react with an electron poor species A substitution
Question 4.2: Write Lewis dot symbols for atoms of the following elements: Mg, Na, B, O, N, Br.
Question 4.1: Explain the formation of a chemical bond. A chemical bond is defined as an attractive force that holds the constituents (atoms, ions etc.) together in a chemical species. Various theories
T3P Propane Phosphonic Acid Anhydride
Technology StrengthS T3P Propane Phosphonic Acid Anhydride The coupling agent of the future Coupling and water removal are synthesis tools that stand at the cutting edge of purity and cost effective manufacture
Chapter 2 Polar Covalent Bonds; Acids and Bases
John E. McMurry http://www.cengage.com/chemistry/mcmurry Chapter 2 Polar Covalent Bonds; Acids and Bases Javier E. Horta, M.D., Ph.D. University of Massachusetts Lowell Polar Covalent Bonds: Electronegativity
Conjugation is broken completely by the introduction of saturated (sp 3 ) carbon:
Conjugation. Conjugation relies on the partial overlap of p-orbitals on adjacent double or triple bonds. ne of the simplest conjugated molecules is 1,3-butadiene. Conjugation comes in three flavors, the
Structure, Mechanism and Reactivity of Hantzsch Esters
Structure, chanism and eactivity of antzsch Esters Jamie Tuttle MacMillan Lab Group eting 08/25/04 Lead eferences: Lavilla,. J. Chem. Soc., Perkin Trans., 2002, 1, 1141. Stout, D. M. and yers, A. I. Chem.
Electrophilic Aromatic Substitution Reactions
Electrophilic Aromatic Substitution Reactions, Course Notes Archive, 1 Electrophilic Aromatic Substitution Reactions An organic reaction in which an electrophile substitutes a hydrogen atom in an aromatic
CHEM 322 Organic Chemistry II - Professor Kathleen V. Kilway
CHEM 322 Organic Chemistry II - Professor Kathleen V. Kilway "Organic Chemistry" by Maitland Jones, 4th edition Chapter 12 Homework: 1, 2, 4, 5, 6, 7, 15, 16, 17, 19, 21, 24, 26, 28, 29, 30, 38, 39, 44,
Syllabus for General Organic Chemistry M07A- Fall 2013 Prof. Robert Keil
Syllabus for General Organic Chemistry M07A- Fall 2013 Prof. Robert Keil Textbook and Materials What you must buy: Organic Chemistry 4 th Ed. Janice G. Smith, McGraw Hill. (Older edition is fine) Chem
EXPERIMENT 17 : Lewis Dot Structure / VSEPR Theory
EXPERIMENT 17 : Lewis Dot Structure / VSEPR Theory Materials: Molecular Model Kit INTRODUCTION Although it has recently become possible to image molecules and even atoms using a high-resolution microscope,
A Grignard reagent formed would deprotonate H of the ethyl alcohol OH.
216 S11-E2 Page 2 Name Key I. (9 points) Answer in the boxes below the following questions for the Grignard reagent C 3 -Mg. (1) (2 points) Is the carbon atom associated with magnesium electrophilic or
Issue in Honor of Prof. O. S. Tee ARKIVOC 2001 (xii) 108-115
Kinetics and mechanism of the base catalyzed cleavage of 2-diazo- 1,3-indandione and the acid catalyzed decomposition of its hydrolysis product, 2-(diazoacetyl)benzoic acid Yvonne Chiang, A. Jerry Kresge,*
Molecules, Compounds, and Chemical Equations (Chapter 3)
Molecules, Compounds, and Chemical Equations (Chapter 3) Chemical Compounds 1. Classification of Elements and Compounds Types of Pure Substances (Figure 3.4) Elements -- made up of only one type of atom
1.- L a m e j o r o p c ió n e s c l o na r e l d i s co ( s e e x p li c a r á d es p u é s ).
PROCEDIMIENTO DE RECUPERACION Y COPIAS DE SEGURIDAD DEL CORTAFUEGOS LINUX P ar a p od e r re c u p e ra r nu e s t r o c o rt a f u e go s an t e un d es a s t r e ( r ot u r a d e l di s c o o d e l a
National Institutes of Health Postdoctoral Fellow, 2008-2011 Harvard University, Boston, MA Research Advisor: Professor E. J.
M. KEVIN BROWN Indiana University Home Phone: 857-498-1640 Department of Chemistry Office Phone: 812-856-9114 800 E. Kirkwood Ave. Bloomington, IN e-mail: brownmkb@indiana.edu APPOINTMENTS Assistant Professor,
2. DECOMPOSITION REACTION ( A couple have a heated argument and break up )
TYPES OF CHEMICAL REACTIONS Most reactions can be classified into one of five categories by examining the types of reactants and products involved in the reaction. Knowing the types of reactions can help
Chapter 7 Substitution Reactions
Chapter 7 Substitution Reactions Review of Concepts Fill in the blanks below. To verify that your answers are correct, look in your textbook at the end of Chapter 7. Each of the sentences below appears
POSS Monomer and Reagent Chemistry Chemistry
PSS Monomer and eagent Chemistry Chemistry Frank J. Feher, aquel Terroba, en-zhi Jin, Sabine Lücke, Frank Nguyen, ichard Brutchey and Kevin D. Wyndham Department of Chemistry UCI Irvine, CA 92697-2025
Syntheses of partially hydrogenated [1,2,4]triazolo[4,5-a] pyrimidine-4-ones through cyclisation of 2-arylidenehydrazino- 6-methyl-4-pyrimidones
![Syntheses of partially hydrogenated [1,2,4]triazolo[4,5-a] pyrimidine-4-ones through cyclisation of 2-arylidenehydrazino- 6-methyl-4-pyrimidones](/thumbs/36/17495609.jpg "Syntheses of partially hydrogenated [1,2,4]triazolo[4,5-a] pyrimidine-4-ones through cyclisation of 2-arylidenehydrazino- 6-methyl-4-pyrimidones")
Issue in onor of Prof. Sándor Antus ARKIVC 2004 (vii) 24-252 Syntheses of partially hydrogenated [1,2,4]triazolo[4,5-a] pyrimidine-4-ones through cyclisation of 2-arylidenehydrazino- 6-methyl-4-pyrimidones
CH 3 CH 2 ONa + H 2 O. CH 3 CH 2 NH 2 + CH 3 OLi
rganic Chemistry Jasperse Acid- Practice Problems A. Identify each chemical as either an acid or a base in the following reactions, and identify conjugate relationships. -You should have one acid and one
Physicochemical Properties of Drugs
Therapeutics I Michael B. Bolger 1/3/02 bjectives: At the end of the next hour: Physicochemical Properties of Drugs 1. The student should be able to calculate the degree of ionization for an acidic or
CHEM 51LB EXP 1 SPECTROSCOPIC METHODS: INFRARED AND NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY
CHEM 51LB EXP 1 SPECTRSCPIC METHDS: INFRARED AND NUCLEAR MAGNETIC RESNANCE SPECTRSCPY REACTINS: None TECHNIQUES: IR Spectroscopy, NMR Spectroscopy Infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy
Brønsted-Lowry Acids and Bases
Brønsted-Lowry Acids and Bases 1 According to Brønsted and Lowry, an acid-base reaction is defined in terms of a proton transfer. By this definition, the reaction of Cl in water is: Cl(aq) + Cl (aq) +
Health Science Chemistry I CHEM-1180 Experiment No. 15 Molecular Models (Revised 05/22/2015)
(Revised 05/22/2015) Introduction In the early 1900s, the chemist G. N. Lewis proposed that bonds between atoms consist of two electrons apiece and that most atoms are able to accommodate eight electrons
Efficient synthesis of 2,4,5-triaryl substituted imidazoles under solvent free conditions at room temperature
General Papers AKIVC 2007 (xvi) 12-18 Efficient synthesis of 2,4,5-triaryl substituted imidazoles under solvent free conditions at room temperature Arshia Parveen, a Md. afi Sk. Ahmed, b Kabeer A. Shaikh,
Asymmetric Formation of Quaternary Carbon Centers Catalyzed by Novel Chiral 2,5-Dialkyl-7-phenyl-7-phosphabicyclo- [2.2.1]heptanes
![Asymmetric Formation of Quaternary Carbon Centers Catalyzed by Novel Chiral 2,5-Dialkyl-7-phenyl-7-phosphabicyclo- [2.2.1]heptanes](/thumbs/25/5320528.jpg "Asymmetric Formation of Quaternary Carbon Centers Catalyzed by Novel Chiral 2,5-Dialkyl-7-phenyl-7-phosphabicyclo- [2.2.1]heptanes")
J. Org. Chem. 1998, 63, 5631-5635 5631 Asymmetric Formation of Quaternary Carbon Centers Catalyzed by Novel Chiral 2,5-Dialkyl-7-phenyl-7-phosphabicyclo- [2.2.1]heptanes Zhaogen Chen, Guoxin Zhu, Qiongzhong
3. What would you predict for the intensity and binding energy for the 3p orbital for that of sulfur?
PSI AP Chemistry Periodic Trends MC Review Name Periodic Law and the Quantum Model Use the PES spectrum of Phosphorus below to answer questions 1-3. 1. Which peak corresponds to the 1s orbital? (A) 1.06
STOICHIOMETRY UNIT 1 LEARNING OUTCOMES. At the end of this unit students will be expected to:
STOICHIOMETRY LEARNING OUTCOMES At the end of this unit students will be expected to: UNIT 1 THE MOLE AND MOLAR MASS define molar mass and perform mole-mass inter-conversions for pure substances explain
The Synthesis of trans-dichlorobis(ethylenediamine)cobalt(iii) Chloride
CHEM 122L General Chemistry Laboratory Revision 2.0 The Synthesis of trans-dichlorobis(ethylenediamine)cobalt(iii) Chloride To learn about Coordination Compounds and Complex Ions. To learn about Isomerism.
AP CHEMISTRY 2007 SCORING GUIDELINES. Question 6
AP CHEMISTRY 2007 SCORING GUIDELINES Question 6 Answer the following questions, which pertain to binary compounds. (a) In the box provided below, draw a complete Lewis electron-dot diagram for the IF 3
Chapter 15 Radical Reactions. Radicals are reactive species with a single unpaired electron, formed by
Chapter 15 Radical Reactions Radicals are reactive species with a single unpaired electron, formed by homolysis of a covalent bond; a radical contains an atom that does not have an octet of electrons,
2. Atoms with very similar electronegativity values are expected to form
AP hemistry Practice Test #6 hapter 8 and 9 1. Which of the following statements is incorrect? a. Ionic bonding results from the transfer of electrons from one atom to another. b. Dipole moments result
Sample exam questions for First exam CHM 2211
Sample exam questions for First exam CM 2211 1. The IR absorption due to the stretching of which of these carbon-hydrogen bonds occurs at the highest frequency? I II III E) V IV V 2. ow many signals would
Calculating Atoms, Ions, or Molecules Using Moles
TEKS REVIEW 8B Calculating Atoms, Ions, or Molecules Using Moles TEKS 8B READINESS Use the mole concept to calculate the number of atoms, ions, or molecules in a sample TEKS_TXT of material. Vocabulary
NaHSO 4 -SiO 2 promoted synthesis of Benzimidazole derivatives
Available online at www.scholarsresearchlibrary.com Archives of Applied Science Research, 2012, 4 (3):1517-1521 (http://scholarsresearchlibrary.com/archive.html) ISS 0975-508X CDE (USA) AASRC9 as 4 -Si
Electrophilic Aromatic Substitution
Electrophilic Aromatic Substitution Electrophilic substitution is the typical reaction type for aromatic rings. Generalized electrophilic aromatic substitution: E E Electrophile Lewis acid: may be or neutral.
Questions on Chapter 8 Basic Concepts of Chemical Bonding
Questions on Chapter 8 Basic Concepts of Chemical Bonding Circle the Correct Answer: 1) Which ion below has a noble gas electron configuration? A) Li 2+ B) Be 2+ C) B2+ D) C2+ E) N 2-2) Of the ions below,
CHM 2210: ORGANIC CHEMISTRY II Third Exam, Form 3 Section 02, Professor A. Herriott November 29, 2007
CM 2210: ORGANIC CEMISTRY II Third Exam, Form 3 Section 02, Professor A. erriott November 29, 2007 No electronic devices (calculators, cell phones, laptops, etc) may be used or consulted during the exam.
RESONANCE, USING CURVED ARROWS AND ACID-BASE REACTIONS
RESONANCE, USING CURVED ARROWS AND ACID-BASE REACTIONS A STUDENT SHOULD BE ABLE TO: 1. Properly use curved arrows to draw resonance structures: the tail and the head of every arrow must be drawn in exactly
Chapter 11 Homework and practice questions Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations
Chapter 11 Homework and practice questions Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations SHORT ANSWER Exhibit 11-1 Circle your response in each set below. 1. Circle the least
Total Organic Synthesis and Characterization of Graphene Nanoribbons
Total Organic Synthesis and Characterization of Graphene Nanoribbons Gang Li Seminar in Dong group 03/26/2014 Content History of Graphene Synthesis and Characterization and Properties of Graphene Conceptual