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Chapter 14: Organometallics, structure and nomenclature. 14.1 – Organometallic nomenclature. Cyclopropyl lithium. Vinyl sodium. Diethyl magnesium. Methyl magnesium iodide Diethylaluminum chloride. 14.2 – Carbon-Metal Bonds in Organometallics. 14.2 – Carbon-Metal Bonds in Organometallics.
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14.1 – Organometallic nomenclature Cyclopropyl lithium Vinyl sodium Diethyl magnesium Methyl magnesium iodide Diethylaluminum chloride
14.2 – Carbon-Metal Bonds in Organometallics Organometallics at YSU Penny Miner, YSU MS (Ricerca Biosciences)
14.2 – Carbon-Metal Bonds in Organometallics Organometallics at YSU Dipolar interactions guide regioselectivity Penny Miner, YSU MS (Ricerca Biosciences)
14.2 – Carbon-Metal Bonds in Organometallics Organometallics at YSU Miner, Wagner, Norris,Heterocycles 2005, 65, 1035-1049
Preliminary Activity Against S. aureus 50-75% decrease in capsule production Prof. Diana Fagan (YSU Biological Sciences)
14.3 – Preparation of Organolithium Compounds Organolithiums
14.4 – Preparation of Organomagnesium Compounds Organomagnesium compounds – Grignard reagents
14.5 – Organolithium Compounds as Bases CH3Li, (CH3)3CLi, 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!
14.6 – Synthesis of Alcohols Using Grignard Reagents Carbonyl Polarization: Grignard Polarization:
14.6-7 – Synthesis of Alcohols Using Organometallic Reagents New Mechanism: Nucleophilic Addition Most often followed by a quench with acid:
14.6-7 – Synthesis of Alcohols Using Organometallic Reagents Overall Sequence: Nucleophilic Addition then quench Very versatile alcohol synthesis
14.6-7 – Synthesis of Alcohols Using Organometallic Reagents Example: Starting material product
14.6-7 – Synthesis of Alcohols Using Organometallic Reagents Example: Starting material product Product IR: 3200 cm-1
14.6-7 – Synthesis of Alcohols Using Organometallic Reagents Product MS: M+ = 254 Starting material product
14.9 – Organic Synthesis – Molecular Engineering DDT, 2003, 1128
14.9 – Molecular Engineering – Designing and Building ACS Petroleum Research Fund Award 2006-2009
14.9 – Retrosynthetic Analysis – Planning the Synthesis Plan Synthesis
14.9 – Retrosynthetic Analysis (synthetic equivalent)
14.9 – Retrosynthetic Analysis (synthetic equivalent)
14.9 – Retrosynthetic Analysis Example:
14.9 – Retrosynthetic Analysis Example:
14.10 – Tertiary Alcohols from Esters and Grignard Reagents Retrosynthesis: Synthesis: Also possible:
14.11 – Alkane Synthesis Using Organocopper Reagents Proposed structure:
14.11 – 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
14.12 – An Organozinc Reagent for Cyclopropane Synthesis Iodomethyl zinc iodide Simmons-Smith reaction
