Chapter 14: Organometallics, structure and nomenclature

Cyclopropyl lithium Vinyl sodiumDiethyl magnesium Methyl magnesium iodide Diethylaluminum chloride 14.1 – Organometallic nomenclature

14.2 – Carbon-Metal Bonds in Organometallics

Penny Miner, YSU MS (Ricerca Biosciences) Organometallics at YSU

14.2 – Carbon-Metal Bonds in Organometallics Penny Miner, YSU MS (Ricerca Biosciences) Organometallics at YSU Dipolar interactions guide regioselectivity

14.2 – Carbon-Metal Bonds in Organometallics Miner, Wagner, Norris, Heterocycles 2005, 65, Organometallics at YSU

50-75% decrease in capsule production Preliminary Activity Against S. aureus Prof. Diana Fagan (YSU Biological Sciences)

14.3 – Preparation of Organolithium Compounds Organolithiums

Organomagnesium compounds – Grignard reagents 14.4 – Preparation of Organomagnesium Compounds

CH 3 Li, (CH 3 ) 3 CLi, n-BuLi are extremely powerful bases Convenient preparation of LDA 14.5 – Organolithium Compounds as Bases

Lab Experiment Grignard Reagent Preparation Glassware must be clean and dry Dry with the “heat gun” Cool then begin experiment Be careful to use the right ether!

14.5 – Organolithium Compounds as Bases

Carbonyl Polarization: Grignard Polarization: 14.6 – Synthesis of Alcohols Using Grignard Reagents

– Synthesis of Alcohols Using Organometallic Reagents New Mechanism: Nucleophilic Addition Most often followed by a quench with acid:

Overall Sequence: Nucleophilic Addition then quench – Synthesis of Alcohols Using Organometallic Reagents Very versatile alcohol synthesis

Example: Starting material product – Synthesis of Alcohols Using Organometallic Reagents

Starting materialproduct Product IR: 3200 cm -1 Example:

Starting materialproduct Product MS: M + = – Synthesis of Alcohols Using Organometallic Reagents

14.8 – Synthesis of Acetylenic Alcohols

14.9 – Organic Synthesis – Molecular Engineering DDT, 2003, 1128

14.9 – Organic Synthesis – Molecular Engineering

14.9 – Molecular Engineering – Designing and Building ACS Petroleum Research Fund Award

14.9 – Retrosynthetic Analysis – Planning the Synthesis

PlanSynthesis

14.9 – Retrosynthetic Analysis (synthetic equivalent)

14.9 – Retrosynthetic Analysis (synthetic equivalent)

14.9 – Retrosynthetic Analysis Example:

14.9 – Retrosynthetic Analysis Example:

14.9 – Retrosynthetic Analysis and Synthesis

14.10 – Tertiary Alcohols from Esters and Grignard Reagents

Retrosynthesis: Synthesis: Also possible: – Tertiary Alcohols from Esters and Grignard Reagents

Proposed structure: – Alkane Synthesis Using Organocopper Reagents

Useful for coupling with primary alkyl halides Use of secondary and tertiary alkyl halides complicated by competing E2 reactions Works for simple alkyl halides, vinyl halides and aryl halides Mechanism not completely understood – Alkane Synthesis Using Organocopper Reagents

Iodomethyl zinc iodide Simmons-Smith reaction – An Organozinc Reagent for Cyclopropane Synthesis

Not covering – 14.17