organic chemistry

32034 ADVANCED ORGANIC CHEMISTRY of 6

COURSE: ADVANCED ORGANIC CHEMISTRY

STUDIES: DEGREE IN CHEMISTRY (2nd cycle)

CODE: 32034

TYPE: TR YEAR: 4th SEMESTER: 1st and 2nd

CREDITS (hours/week): 9,0 ECTS CREDITS: 7,5 PROFESSOR: Dr. Jordi Teixidó Closa LANGUAGE: Catalan PREREQUIREMENTS: Organic Chemistry, Inorganic Chemistry, Physical Chemistry, Biochemistry. PREVIOUS KNOWLEDGES: The ones corresponding to prerequirement courses, in particular those acquired in Organic Chemistry. COURSES THAT HAVE TO BE STUDIED SIMULTANEOUSLY: COURSE DESCRIPTION: After learning the basic knowledges in Organic Chemistry of first cycle, the student has to face an expansion of the traditional elements (reactions and mechanisms) as well as the most current procedures of general application in the range of Organic Chemistry. The student will be taught how to recognize, analyse and design those usual procedures employed traditionally in the modern Organic Chemistry. This course is divided in 3 blocks. In the first block (chapter 1) concepts like isomerism, stereoisomerisms and structural analysis, structure and reactivity are studied. In the second big block (chapters 2-7) it is deeply studied the reactivity of organometallic chemistry and organyl compounds in the periodic table. The third block (chapters 8-9) is dedicated to the structure, formation and reactivity of cycles and heterocycles. All this has the objective to give the student a solid multidisciplinary base in applications that go from the materials and polymers science, through biochemistry and natural products to the pharmaceutical medical chemistry. COURSE OBJECTIVES:

1. Supply the students with the knowledges of modern Organic and Organometallic Chemistry necessary for Chemistry practice [1, 5, 7].

2. Teach and apply the inductive-deductive method to problems solution in Organic and Organometallic chemistry (Retrosynthetical analysis, mechanisms and prediction of reaction products, etc.) [2, 3].

3. Analyse the impact of Organic and Organometallic Chemistry in the development of the society [4].

CONTENTS: Block I: Organic Stereochemistry.


1. Organic Stereochemistry.

1.1 Isomerism Classification. Isomers. 1.2 Stereoisomers: Enantiomers, Diastereomers and Atropisomers. Nomenclature 1.3 Structural diastereomers . 1.4 Resolution. 1.5 Non-configurational diastereomers: cis-trans, cis-trans in rings, in-out. 1.6 Homotopic, enantiotopic and diastereotopic atoms, groups and sides. 1.7 Asymmetric synthesis, examples. 1.8 Conformational analysis.

Block II: Organic chemistry through periodic table.

2. Group VA (N, P).

2.1 Nitrogen. 2.1.1 Review of the reactivity of aliphatic and aromatic amines,

diazonium salts and aromatic nitro. 2.1.2 Enamines. 2.1.3 Mannich. 2.1.4 Vilsmeier-Haack. 2.1.5 Baylis-Hillman 2.1.6 Shapiro.

2.2 Phosphorus. 2.2.1 Achievement. 2.2.2 Achievement of halogenated derivates. Phosphonium salts. 2.2.3 Wittig. 2.2.4 Carbodiimides formation.

3. VIA (S, Se,...) groups

3.1 Sulphur 3.1.1 Nomenclature. 3.1.2 Thiols (mercaptanes). 3.1.3 Sulphurs and thioethers 3.1.4 Sulfoxides and sulfones 3.1.5 Sulfonic, sulfinic, sulfenic acids and derivates. 3.1.6 Thiocarbonylic acids.

3.2 Selenium 3.2.1 Reactivity.

4. Organometallic and organyls. Achievement, structure and reactivity in Organic Chemistry.

4.1 Types of bond. 4.2 Achievement. 4.3 Organometallic compounds of the IIA and IIB (Mg, Zn, Cd, Hg,...) groups

4.3.1 Organomagnesian. 4.3.2 Organozínc. 4.3.3. Organocadmium.


4.3.4 Organomercurial.

4.4 Organometallic compound of the IA y IB (Li, Na, K, Cu, Ag, Au,...) groups 4.4.1 Organosodium and potassium. 4.4.2 Organolithium. 4.4.3 Organocupper. 4.4.4 Organocuprates of terminal alkynes.

4.4.5 Organometallic compounds of silver and gold

5. IIIA (B, Al, Tl,...) group

5.1 Boranes. 5.1.1 Hydroboration. 5.1.2 Structure and reactivity. 5.1.3 Reactions.

5.2 Alanes. 5.3 Gallium, Indium, Thallium

6. IVA (C, Si, Ge, Sn, Pb,...) group

6.1 Carbon group. 6.2 Organosilanes. 6.2.1 Achievement 6.2.2 General reactivity. 6.2.3 Silyl-ethers Alcohol protection. 6.2.4 Silyl-enol-ethers. Enols capture-protection. 6.2.5 SE vinylsilanes. 6.2.6 Peterson olefination 6.2.7 Epoxy and allyl silanes. 6.3 Stannates.

6.3.1 Stille and allyl addition. 7. Transition metals and catalysis (Groups III-VIII B)

7.1 Pd chemistry. Kumada and Neguishi Suzuki, Stille, Heck, Sonogashira, Buchwald-Hartwig reactions, reactions with π-allyl complexes, terminal olefins oxidation.

7.2 Ni chemistry. Homocouplings, macrocyclations, allylations, N-T-H-K reactions, carbonylation of Reppe.

7.3 Rh chemistry. Hydrogenations, Montsanto process. 7.4 Co chemistry. Alkyne protector, Pauson-Khand, alkyne trimerization,

oxidations, olefin isomerizations. 7.5 Fe chemistry. Collman reactive, enolic condensations, diene protection, Noyori

ringing, Shift process. 7.6 Cr chemistry. SEAr reactions, Fisher carbenes, Dötz reaction. 7.7 Os chemistry. Dihydroxylation. 7.8 Ru chemistry. Metathesis reactions: RCM, ROMP, ADMET. 7.9 V chemistry. Catalytic epoxidations with V. 7.10 Ti chemistry. Olefination, asymmetric epoxidation of Sharpless, Mc Murry

reaction, Diels-Alder catalyst, aldol condensations. 7.11 Mn chemistry. Enantioselective epoxidation with complexes.


7.12 Zr chemistry. Hydrozirconium, carbometallation, bicyclations. 7.13 La chemistry. Biheterometallic catalysts LLB.

Block III: Carbocycles and heterocycles.

8. Formation of carbocyclic systems.

8.1 Intramolecular and intermolecular construction 8.2 Intramolecular. Baldwin rules 8.3 Intermolecular construction. Pericyclic reactions.

8.3.1 Boundary orbitals. 8.3.1.1 Cycloaddition. 8.3.1.2 Electrocyclic. 8.3.1.3 Sigmatropic

8.3.2 Pericyclic reactions. Formation of 3 member rings. 8.3.3 Pericyclic reactions. Formation of 4 member rings . 8.3.4 Pericyclic reactions. Formation of 5 member rings . 8.3.5 Pericyclic reactions. Formation of 6 member rings .

9. Heterocyclic Chemistry.

9.1 Nomenclature. 9.2 Synthesis and heterocycles reactivity.

9.2.1 Rings of 3. 9.2.1.1 Synthesis 9.2.1.2 Reactivity.

9.2.2 Rings of 4. 9.2.2.1 Synthesis 9.2.2.2 Reactivity.

9.2.3 Rings of 5, 6 (Aromatic). 9.2.3.1 Synthesis. Intramolecular cycling 9.2.3.2 Synthesis. Intermolecular cycling. 9.2.3.3 Synthesis. The CN group. 9.2.3.4 Synthesis. Polyheteroatomic reactives. 9.2.3.5 Synthesis. Cycloaddition [4+2]. Cycloaddition [3+2] 9.2.3.6 Reactivity heterocycles, rings of 5 and 6: pyridine,

quinoline, isoquinoline, pyrimidine, pyrrol, imidazol, furan, thiophene etc.


METHODOLOGY: On one hand, the course is given essentially in master classes where it is introduced and discussed the most relevant part of the teaching material previously supplied to the student. There are multimedia tools to improve the visualization of tridimensional and mechanical aspects (stereochemistry). Each chapter includes a series of problems /questions that the student must solve /analyse individually at home and that will be discussed in practical sessions. In these practical sessions different synthetic processes, strategies, reactives and mechanisms will also be analysed and discussed, with the objective that the student strengthens his ability to manage the concepts learnt. EVALUATION: A. Exams C. Test exams J. Participation in class

The student must make 2 scheduled partial exams (end of first and second term) and 2 additional exams in class of the chapters 1 (stereochemistry) and 7 (transition metals) at about the middle of the respective terms (end of November and beginning of April).The course can then be passed with the consequential average qualification of these partial exams or a good qualification in any of the final exams scheduled in the respective dates.

CRITERIA FOR RESULTS EVALUATION:

Objective 1: • The student must demonstrate ability to understand/solve/discuss questions referring

tridimensional properties (stereochemistry) and molecules reactivity [A, C, J]. • The student must demonstrate inductive-deductive ability to understand /solve

/discuss theoretical questions in the light of the principles of Organic Chemistry[A,J]. • The student must show ability o foresee and interpret the results of organic,

organometallic and heterocyclic chemical reactions [A, C, J]. Objective 2:

• The student must demonstrate ability to develop synthetic routes for organic molecules by means of integrated application of the methodologies learnt (stereochemistry, organometallic chemistry, heterocyclic chemistry, “step backwards” method, etc. ) [A,J].

Objective 3: • The student must demonstrate the knowledge of some of the most relevant industrial

processes in the environment of Organic and Organometallic Chemistry [A,J]. ORDINARY BIBLIOGRAPHY:

• M.B. Smith, J. March, March’s Advanced Organic Chemistry. Reactions, Mechanisms, and Structure, John Wiley & Sons, 5th ed., New York, 2001. ISBN: 0471585890

• E.L. Eliel, S.H. Wilen, M.P. Doyle, Basic Organic Stereochemistry, Wiley-Interscience, John Wiley & Sons, New York, 2001. ISBN: 047137499

• Ch. Elschenbroich, A. Salzer, Organometallics. Wiley-VCH, 1989.ISBN: 0895738686

• J.A. Joule, K. Mills, Heterocyclic Chemistry, 4th Ed., Blackwell Science Inc., 2000, ISBN: 0632054530


• W. Reusch ([email protected]), Virtual Textbook of Organic Chemistry, http://www.cem.msu.edu/~reusch/VirtualText/intro1.htm, (30-9-2002).

• Web of the course: http://sintesi-gem.iqs.edu/qoa BIBLIOGRAPHY or COMPLEMENTARY MATERIAL:

• R.K. Mackie, D.M. Smith, R.A. Aitken, Guidebook to Organic Synthesis, 3rd. Ed., Pearson PTP, 2000. ISBN: 0582290937

• J. McMurry, Organic Chemistry (5th edition), Brooks/Cole Publishing Company, Pacific Grove, California, 2000. ISBN: 0534373674

• A.R. Katritzky, A.F. Pozharskii, Handbook of Heterocyclic Chemistry, Pergamon Press; 2nd edition, 2000, ISBN: 0080429890

• S. Seyhan. Química Orgánica.Tomos 1 y 2. Ed. Reverté, 1997. • R. T. Morrison, R. N. Boyd, Organic Chemistry (6th edition), Prentice Hall International

Inc, New Jersey, 1992 • E. Fernández, F. Fariña, Nomenclatura de la Química Orgánica (Secciones A, B, C, D,

E, F y H), CSIC-RSEQ, Madrid, 1987 • A. Messeguer, M. A. Pericás, Nomenclatura de Química Orgànica (Seccions A, B i C),

CSIC-Institut d'Estudis Catalans, Barcelona, 1989

• J. I. Borrell, J. Teixidó, J. L. Falcó, Síntesis Orgánica, ed. Síntesis, Madrid, 1999.

• G. Procter, Asymmetric Synthesis, Oxford University Press, Oxford 1996.

• M. B. Smith. Organic Synthesis, 2nd Ed., Mc Graw-Hill, New York, 2001.

• G.O. Spessard, G.L. Miessler, Organometallic Chemistry, Prentice Hall, 1996.

• F. Diederich and P.J. Stang (Editors), Metal-catalyzed Cross-coupling Reactions, Wiley-VCH, 1998.

• K. Weissmerl, H.J. Arpe, Industrial Organic Chemistry, Wiley-VCH, 1997 PREPAIRED BY: Dr. Jordi Teixidó Closa DATE OF THE LAST REVIEW: January 2005

organic chemistry

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