Chapter 14: Organometallics, structure and nomenclature H CR3

Chapter 14: Organometallics, structure and nomenclature H CR3 - + Cl CR3 radical chemistry carbon electrophiles + M CR3 carbon nucleophiles 14.1 Organometallic nomenclature Li H

CH2=CHNa Cyclopropyl lithium Vinyl sodium CH3MgI Methyl magnesium iodide (CH3CH2)2Mg Diethyl magnesium (CH3CH2)2AlCl Diethylaluminum chloride 14.2 Carbon-Metal Bonds in Organometallics 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 0.9

HO HO HO O OH N N N (CH2)7CH3 0.8 0.7 H Absorbance at 450 nm

0.6 0.5 50 L EtOH 1 L MV-II-065 0.1 L MV-II-065 0.01 L MV-II-065 0.4 0.3 50-75% decrease in capsule production Prof. Diana Fagan (YSU Biological Sciences) 0.2

0.1 0 100 200 400 Reciprocal of Antibody Dilution 800 14.3 Preparation of Organolithium Compounds R X +2M 2 Li Cl

ether -30 oC Br 2 Li ether 35 oC RM + M+X- Li Li + LiCl + LiBr Organolithiums

14.4 Preparation of Organomagnesium Compounds R X + Mg RMgX Mg Br Br ether RT Mg ether 35oC MgBr MgBr

Organomagnesium compounds Grignard reagents 14.5 Organolithium Compounds as Bases CH3Li, (CH3)3CLi, n-BuLi are extremely powerful bases N H + THF Li N Li +

o - 78 C Convenient preparation of LDA H 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

14.6 Synthesis of Alcohols Using Grignard Reagents Carbonyl Polarization: O Grignard Polarization: O - MgBr 14.6-7 Synthesis of Alcohols Using Organometallic Reagents New Mechanism: Nucleophilic Addition - MgBr

O OMgBr Most often followed by a quench with acid: OMgBr H3O+ OH 14.6-7 Synthesis of Alcohols Using Organometallic Reagents Overall Sequence: Nucleophilic Addition then quench 1. Mg, ether Br 2. (CH3) 2C=O 3. H3O+ Very versatile alcohol synthesis

OH 14.6-7 Synthesis of Alcohols Using Organometallic Reagents Br Example: CH2OH 1. Mg, ether 2. H2C=O 3. H3O+ Starting material 7 6 5

4 PPM 3 product 2 1 0 7 6 5

4 PPM 3 2 1 0 14.6-7 Synthesis of Alcohols Using Organometallic Reagents Cl Example: 2. CH3CHO 3. H3O+ Starting material

70 60 50 40 OH 1. Mg, ether PPM 30 20 10

0 80 product 70 60 50 40 PPM 30 Product IR: 3200 cm-1

20 10 0 14.6-7 Synthesis of Alcohols Using Organometallic Reagents Br OH 1. Mg, ether Product MS: M+ = 254 2. Ph2C=O 3. H3O+ Starting material 3

product 2 PPM 1 0 7 6 5 4 PPM 3

2 1 0 14.8 Synthesis of Acetylenic Alcohols H3C H 1. NaNH2 H3C 2. H2C=O 3. H3O+ O

CH2OH H3C 1. H3C 2. H3O+ Li OH 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 2006-2009

14.9 Retrosynthetic Analysis Planning the Synthesis Target molecule Precursors 14.9 Retrosynthetic Analysis Planning the Synthesis Plan Synthesis 14.9 Retrosynthetic Analysis Target molecule RMgX or RLi = R OH

Precursors (synthetic equivalent) O + CH 3M 14.9 Retrosynthetic Analysis H R C OH H H R: H O

RMgX or RLi = R (synthetic equivalent) CH3 R C OH H CH3 R C OH CH3 H3C R: H H3C R:

H3C O O 14.9 Retrosynthetic Analysis Example: OH MgBr O + more accessible H CH3MgBr

+ O H 14.9 Retrosynthetic Analysis Example: OH MgBr O + H O H

+ BrMg 14.9 Retrosynthetic Analysis and Synthesis H OH O MgBr + 1. Mg, THF Br 2. H

3. H3O+ O OH Br 14.10 Tertiary Alcohols from Esters and Grignard Reagents 2 R MgX O + H3C OCH3

then H3O+ O 2 MgBr 2 R CH3 THF then H3O+ OH O

MgBr + R OH OCH3 + OH THF OCH3 THF then H3O+ 3o alcohol

14.10 Tertiary Alcohols from Esters and Grignard Reagents O OH Retrosynthesis: Synthesis: Also possible: 2 CH3MgBr + H3CO OH 1. Mg, THF CH3Br

OH 2. PhCO2CH3 (0.5 eq) 3. H3O+ O + MgBr 14.11 Alkane Synthesis Using Organocopper Reagents ether or THF 2 RLi + CuX R2CuLi + LiX Proposed structure: R

Cu Br (CH3CH2CH2CH2)CuLi ether or THF R Li 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 ether Works for(CHsimple alkyl halides, vinyl halides

CH3(CH2)8and CH2CHaryl 3)2CuLi + CH3(CH2)8CH2I 3 halides 0oC Mechanism not completely understood 14.12 An Organozinc Reagent for Cyclopropane Synthesis CH2I2 + Zn ether

H I C ZnI H Iodomethyl zinc iodide I-CH2-ZnI H C H IZn I Simmons-Smith reaction C H H Not covering 14.13 14.17

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