In this course I will deal, in detail, of some of the modern and important methods/aspects of (a) Oxidation (b) Reduction and (c) C-C Bond Formation with special emphasis on addressing (i) Selectivity [Regio-, Chemo- and Stereo- (Enantio- and Diastereoselectivity)] (ii) Mechanism (iii) Stereochemistry (wherever necessary) and (iv) Application in solving some synthetic problems using the synthetic reactions discussed Note: (1) I will give appropriate references of books, research papers, and reviews for people for extra information as and when they need. (2) It is expected that this course will help MSc students appearing for NET, GATE and GRE/AGRE examinations. It will also help chemists working in industry who use such reactions in their daily work. INTENDED AUDIENCE :MSc in ChemistryPREREQUISITES : BSc (Chemistry: specially organic chemistry courses)INDUSTRIES SUPPORT :Dr. Reddy’s Laboratory, Syngene, Bristol-Myers Bangalore, Syngenta (Goa), Pharma Industries
Essentials of Oxidation, Reduction and C-C Bond Formation. Application in Organic Synthesis
Indian Institute of Technology Bombay and NPTEL via Swayam
Overview
Syllabus
Week 1:Lecture 1: Introduction to organic synthesis, importance of selectivity and basics of oxidation of alcohols and development of sulfur based oxidations: Swern oxidation and related concepts
Lecture 2: Continuation of Swern oxidation and the utility of intermediates derived from Swern oxidation including Pummerer intermediates Lecture 3. Oxidations using selenium compounds such as SeO2 and organoselenium compoundsWeek 2:Lectures 4 and 5: Dess-Martin, IBX and related hypervalent iodine based oxidations
Lecture 6: Silver carbonate/celite, Prevost reactions and its modern variation. Microbial oxidations such as Pseudomonas Putida etc. Week 3:Lecture 7: Oxidations with RuO4 and other Transition metal catalysed oxidations
Lecture 8: Tamao-Fleming Oxidation
Lecture 9: Oxidations with Dimethyl dioxirane (DMDO) and 2-sulfonyloxaziridines and chiral versions
Lecture 10:Oxidations at unfunctionalised carbons, Photosensitized oxidations Week 4:Lectures 11-14: Reduction of Carbonyl compounds with Boron and Aluminium based reagents such as Luche Reduction, NaCN(BH3), DIBAL, Red-Al, L-and K-Selectrides, Superhydrides and associated selectivities.
Week 5:Lecture 15: Low Valent Titanium species and Microbial reductions (NADH model etc.)
Lecture 16: Dissolving Metal Reductions
Lecture 17: Reduction with Silanes Week 6:Lectures 18 and 19: Sharpless epoxidation and synthetic utility of the chiral epoxy alcohols
Lecture 20: Katsuki-Jacobsen epoxidation and mechanistic details
Lectures 21 : OsO4 based and related Sharpless Asymmetric Dihydroxylation Week 7:Lecture 22: Corey’s oxazaborilidines in asymmetric reductions
Lecture 23: Noyori’s Ruthenium catalysed reduction of ketones
Lecture 24: Asymmetric Hydrogenations with BINAP Week 8:Lecture 25: C-C Bond formation via Carbanions alpha to electron withdrawing groups
Lecture 26: Boron and Silicon Enolates: Formation and Use in C-C Bond Formation
Lecture 27: Imines in C-C Bond Formation
Lecture 28: Simmons-Smith Cyclopropanation in Organic Synthesis
Week 9:Lectures 29-32: Use of Allyl Boron, Allyl and Vinyl Silanes and Allyl Tin compounds in C-C Bond FormationWeek 10:Lecture 33: Introduction to SAMP and RAMP chiral ligands for asymmetric C-C bond formation
Lecture 34: Introduction to Oppolzer’s Sultam based chiral ligands and their reactions for organic synthesis
Lectures 35 and 36: Evans’ Oxazolidinone for asymmetric synthesis Week 11:Lectures 37 and 38: Synthesis of selected natural products using above discussed methods of oxidation, reduction and C-C Bond formationsWeek 12:Lectures 39 and 40: Synthesis of selected natural products using above discussed methods of oxidation, reduction and C-C Bond formations
Lecture 2: Continuation of Swern oxidation and the utility of intermediates derived from Swern oxidation including Pummerer intermediates Lecture 3. Oxidations using selenium compounds such as SeO2 and organoselenium compoundsWeek 2:Lectures 4 and 5: Dess-Martin, IBX and related hypervalent iodine based oxidations
Lecture 6: Silver carbonate/celite, Prevost reactions and its modern variation. Microbial oxidations such as Pseudomonas Putida etc. Week 3:Lecture 7: Oxidations with RuO4 and other Transition metal catalysed oxidations
Lecture 8: Tamao-Fleming Oxidation
Lecture 9: Oxidations with Dimethyl dioxirane (DMDO) and 2-sulfonyloxaziridines and chiral versions
Lecture 10:Oxidations at unfunctionalised carbons, Photosensitized oxidations Week 4:Lectures 11-14: Reduction of Carbonyl compounds with Boron and Aluminium based reagents such as Luche Reduction, NaCN(BH3), DIBAL, Red-Al, L-and K-Selectrides, Superhydrides and associated selectivities.
Week 5:Lecture 15: Low Valent Titanium species and Microbial reductions (NADH model etc.)
Lecture 16: Dissolving Metal Reductions
Lecture 17: Reduction with Silanes Week 6:Lectures 18 and 19: Sharpless epoxidation and synthetic utility of the chiral epoxy alcohols
Lecture 20: Katsuki-Jacobsen epoxidation and mechanistic details
Lectures 21 : OsO4 based and related Sharpless Asymmetric Dihydroxylation Week 7:Lecture 22: Corey’s oxazaborilidines in asymmetric reductions
Lecture 23: Noyori’s Ruthenium catalysed reduction of ketones
Lecture 24: Asymmetric Hydrogenations with BINAP Week 8:Lecture 25: C-C Bond formation via Carbanions alpha to electron withdrawing groups
Lecture 26: Boron and Silicon Enolates: Formation and Use in C-C Bond Formation
Lecture 27: Imines in C-C Bond Formation
Lecture 28: Simmons-Smith Cyclopropanation in Organic Synthesis
Week 9:Lectures 29-32: Use of Allyl Boron, Allyl and Vinyl Silanes and Allyl Tin compounds in C-C Bond FormationWeek 10:Lecture 33: Introduction to SAMP and RAMP chiral ligands for asymmetric C-C bond formation
Lecture 34: Introduction to Oppolzer’s Sultam based chiral ligands and their reactions for organic synthesis
Lectures 35 and 36: Evans’ Oxazolidinone for asymmetric synthesis Week 11:Lectures 37 and 38: Synthesis of selected natural products using above discussed methods of oxidation, reduction and C-C Bond formationsWeek 12:Lectures 39 and 40: Synthesis of selected natural products using above discussed methods of oxidation, reduction and C-C Bond formations
Taught by
Prof. Yashwant D Vankar
