C-C bond forming reactions Known C-C bond forming reactions (New C-C bond forming reactions in KJM3200) Organometallic coupling C-C bond forming reactions.

Slides:

Advertisements

Similar presentations

Based on McMurry’s Organic Chemistry, 7th edition

Advertisements

Oxidation-Reduction & Organometallic

Chemistry of Carbonyl Compounds (McM 19-12) Nucleophilic addition / substitution May also be acid cat.

Based on McMurry’s Organic Chemistry, 7th edition

Chapter 10. Alkyl Halides. What Is an Alkyl Halide An organic compound containing at least one carbon-halogen bond (C-X) –X (F, Cl, Br, I) replaces H.

10. Alkyl Halides Based on McMurry’s Organic Chemistry, 6 th edition.

Carbanions: Formation and Reactions Part 1. The C-C bonds of a molecule under construction constitute its scaffolding. Reactions which form new C-C bonds.

Carbon-Carbon Bond Forming Reactions

Organometallic Compounds Chapter 15. Carbon Nucleophiles: Critical in making larger organic molecules. Review some of the ones that we have talked about….

15-1 Organometallic Compounds Chapter Organometallic Compounds  Organometallic compound:  Organometallic compound: A compound that contains.

Chapter 111 Organometallic Compounds: Chapter 11.

Organic Chemistry William H. Brown & Christopher S. Foote.

Synthesis of Alcohols Reduction of Aldehydes and Ketones Common reducing agents and conditions: NaBH 4 ( sodium borohydride ) alcohol, ether, or H 2 O.

Compounds that contain _________________bond (______): Examples of M include ________(Grignard reagents), _____________. ____________ carbon: Reacts with.

CHE 242 Unit V Structure and Reactions of Alcohols, Ethers and Epoxides; Basic Principles of NMR Spectroscopy CHAPTER TEN Terrence P. Sherlock Burlington.

Aldehydes from oxidation of primary alcohols using the Dess- Martin periodinane reagent 14.2 Preparing Aldehydes and Ketones.

Alcohols: Structure & Synthesis

The Nobel Prize in Chemistry 2010 "for palladium-catalyzed cross couplings in organic synthesis". Photo: University of Delaware, USA Photo: Purdue University,

Carbanions | — C: – | The conjugate bases of weak acids, strong bases, excellent nucleophiles.

John E. McMurry Paul D. Adams University of Arkansas Chapter 10 Organohalides.

Chapter 10 Structure and Synthesis of Alcohols

Reactions of Aromatic Compounds

Lecture 14 APPLICATIONS IN ORGANIC SYNTHESIS Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

CH105.2 Part 1: Problem Solving in Organic Chemistry Carbon Intermediate Types.

Organometallic Reagents: Sources of Nucleophilic Carbon for Alcohol Synthesis 8-7 If the carbonyl carbon of an aldehyde or ketone could be attacked by.

OrgChem- Chap20 1 Chapter 20 Enolates / Other Carbon Nucleophiles C-C bond formation is very important  larger, more complex organic molecule can be made.

I. Organometallic Reagents = carbon-metal bonds

Topics: Grignard reagents and electrophiles

Reduction of Aldehydes and Ketones Reduction of Aldehydes and Ketones to Alcohols.

VUOS COMPANY PROFILE PARTNER FOR COOPERATION Cross coupling reactions.

Pd-Catalyzed C-C Coupling Rxns Stille coupling: Negishi coupling: Suzuki coupling: Heck reaction: Sonogashira coupling:

Alkenes: Reactions with carbenes (McM 7.6) cont. Alkenes: Addition of radicals etc - Polymerisation (McM 7.10, 14.7) Alkenes:Formation by elimination reactions.

Chapter 15 Reagents with Carbon-Metal Bonds

Ch. 18 Lect. 2 Complex Carbonyl Reactions I.Aldol Condensation A.Two aldehyde molecules can react to form an  -unsaturated aldehyde product 1)This reaction.

© 2011 Pearson Education, Inc. 1 Organic Chemistry 6 th Edition Paula Yurkanis Bruice Chapter 18 Carbonyl Compounds II Reactions of Aldehydes and Ketones.

Alkyne Reactions I.Reduction of Alkynes A.Relative Reactivity of 2  -bonds Alkynes react like alkenes, but twice a)Hydrogenation of alkynes goes to alkanes.

Synthesis Biosynthesis Reagents = small carbon-based molecules (e.g. amino acids, carbohydrates) Catalysts = enzymes, proteins that bind and then catalyze.

1 FIVE METHODS OF PREPARING ALCOHOLS. 2 5 METHODS OF PREPARING ALCOHOLS 1. Hydroxide ions (OH - ) replace halogens in unhindered alkyl halides (Me° and.

11.1 Organometallic Compounds (R-M) Organomagnesium & Organolithium compds 15.1 Lithium Diorganocopper (Gilman) Reagents 15.2 No t covered: Organopalladium.

Renee Y. Becker CHM 2210 Valencia Community College

Organometallic Compounds

Spring 2011Dr. Halligan CHM 236 Organometallic Compounds Chapter 11.

Properties of ,  -Unsaturated Aldehydes and Ketones 18-8 Conjugated unsaturated aldehydes and ketones are more stable than their unconjugated isomers.

FURAN The least aromatic 5-membered ring Reaction with electrophiles - Protonation Conc. H 2 SO 4 Lewis acids (i.e. AlCl 3 ) Decomp.

Chapter 18 Additions to the Carbonyl Group Reactions of Aldehydes and Ketones.

John E. McMurry Paul D. Adams University of Arkansas Chapter 10 Organohalides.

KJM Organic Chemistry II Form of teaching Laboratory course (120 hours) Lectures (20 hours). Colloquiums (10 hours.) Form of exam Written exam (3.

10. Alkyl Halides. 2 What Is an Alkyl Halide An organic compound containing at least one carbon- halogen bond (C-X) X (F, Cl, Br, I) replaces H Can contain.

10. Alkyl Halides Based on McMurry’s Organic Chemistry, 6 th edition ©2003 Ronald Kluger Department of Chemistry University of Toronto.

John E. McMurry Paul D. Adams University of Arkansas Chapter 10 Organohalides.

Oxidation-Reduction & Organometallic

Carbanions | — C: – The conjugate bases of weak acids,

Organometallic Compounds

Chapter 10 Organohalides

Chapter 10 Organohalides

Chapter 2. Cross-coupling Reactions

Chapter 10 Organohalides.

Carbon-Carbon Bond Formation and Synthesis

Properties Nomenclature Preparation Reactions Synthesis

CH 12-3: Grignard Reaction-I

Chapter 10 Organohalides

Reactions with electrophiles at C

Chap. 4. C-C Bonds with Unstabilized Carbanions

Chapter 20 Introduction to Carbonyl Chemistry; Organometallic Reagents; Oxidation and Reduction.

Based on McMurry’s Organic Chemistry, 7th edition

Based on McMurry’s Organic Chemistry, 7th edition

10. Alkyl Halides Based on McMurry’s Organic Chemistry, 6th edition

Based on McMurry’s Organic Chemistry, 7th edition

Chapter 10 Organohalides

Presentation transcript:

C-C bond forming reactions Known C-C bond forming reactions (New C-C bond forming reactions in KJM3200) Organometallic coupling C-C bond forming reactions Protecting groups in organic synthesis

Addition to carbonyl groups

See also lab ex 6

Conjugate addition Nucleophilic addition to alkenes (chapt. 23) Conjugate add., 1,4-add., Michael add.

Alkylation  to C=O (also for instance RR 2 CHCN) (new)

Electrophilic aromatic substitution Alkylation of alkynes

Cycloadditions Rearrangements (chapt. 30, in the end of this course )

C-C Bond Formation - Organometallic Coupling Reactions (McM 10.9, Lab ex 10)

Grignard reagents and Organolithium reagents Reacts with carbonyls Strong bases RMgX or RLi does not react well with alkyl halides in substitutions

Organocuprates (McM 10.9) Gilman reagent Dialkylcuprate Participate in substitution with alkylhalides (Cl, Br, I) (R: alkyl, alkenyl, alkynyl, aryl) Mech. see next slide

Also reaction with alkenyl halides and arylhalides (sp 2 ) Not S N 1 or S N 2

Palladium catalyzed coupling reactions (Lab ex. 10) R’-Met: R’ZnX - Negishi coupling - Esp. good for R’ = alkyl, R’ZnX generated in situ R’SnBu 3 / R’SnMe 3 - Stille coupling -R’ (alkynyl) aryl, alkenyl, organotin comp. tox R’SnBu 3 / R’SnMe 3 stable R’B(OH) 2 / R’B(OR) 2 - Suzuki coupling - R’ (alkynyl) aryl, alkenyl, Green react. R’B(OH) 2 / R’B(OR) 2 relatively stable react. requires base R’MgX - Kumada coupling Less reactive, often Ni-cat. (less stable than Pd-cat)

General mechanism Met: -ZnX, -B(OH) 2, -SnR 3 (-MgX) Alkenyl or aryl halides Pd complex from aklyl halides unstable Alkynyl, alkenyl, aryl, alkyl reacts (depending on the metal used)

The Suzuki reaction

Special cases - No preformed R’Met Coupling on alkynes - Sonogashira coupling Coupling on alkenes - Heck coupling (Somewhat diff. mech.)

Why difficult to couple alkyl halides

Protecting groups (PG) in organic synthesis (McM 17.9)

Examples Protection of ROH (McM 17.9)

Other ex. of ROH protecting groups (not mentioned in McM) esters also for prot. of acids

Protection of aldehydes / ketones (McM 19.11) Two extra steps The protecting group curse