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Chapter 14
carbon-metal bonds
14.1: Organometallic Nomenclature (please read)
H H
H3CH2CH2CH2C-Li C C (H3C)2Cu- Li+
H MgBr
Butyllithium vinylmagnesium bromide Dimethylcopper lithium
C X C MgX
!+ !- !- !+ _
C X C MgX C
Alkyl halides will react with some metals (M0) in ether or THF to
form organometallic reagents
14.3: Preparation of Organolithium Compounds
Organolithium Compounds
2 Li(0)
R-X R-Li + LiX
diethyl ether
!- !+ _
very strong bases
C Li C
very strong nucleophiles
M(0) H2 O
R-X R-M R-H + M-OH
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14.4: Preparation of Organomagnesium Compounds:
Grignard Reagents
Mg(0)
R-X R-MgX (Grignard reagent)
THF
R-X can be an alkyl, vinyl, or aryl halide (chloride, bromide,
or iodide)
Solvent: diethyl ether (Et2O) or tetrahydrofuran (THF)
H3CH2C CH2CH3
O
O
diethyl ether (Et2O) tetrahydrofuran (THF)
Mg0 _
H3O+
HO Br HO MgBr O H HO H
_ BrMg
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14.5: Organolithium and Organomagnesium Compounds
as Brønsted Bases - Grignard reagents (M = MgX) and
organolithium reagents (M = Li) are very strong bases.
R-M + H2O R-H + M-OH
pKa pKa
(CH3)3C-H 71 H2N-H 36
H3CH2C-H 62 H C C H 26
H3C-H 60 Water 16
H H
C C 45
H H
H H
H H
43
H H
terminal
butyllithium lithium pKa > 60
acetylene
acetylide
(pKa ~ 26)
THF
R C C H + H3C-H2C-MgBr R C C MgBr + H3C-H2C-H
ethylmagnesium magnesium
bromide acetylide
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Grignard reagents react with . . .
formaldehyde (H2C=O) to give primary alcohols
Br Mg0, ether MgBr 1) H2C=O
2) H3O+ OH
ether
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14.7: Synthesis of Alcohols Using Organolithium Reagents
Organolithium reagents react with aldehydes, ketones, and
esters in the same way that Grignard reagents do.
Li
O ether O H3O+ OH
+ R-Li
C C C
R R
pKa~ 26 pKa~ 36
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THF OH
O
_ + R1 C C C
R1 C C MgBr + C
then H3O+
R
R2 R3 R2 3
acetylenic alcohol
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14.9: Retrosynthetic Analysis - the process of planning a
synthesis by reasoning backward from the the target molecule
to a starting compound using known and reliable reactions.
OH
2-Phenyl-2-propanol CH3
CH3
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14.11: Alkane Synthesis Using Organocopper Reagents
ether H3C _
2 CH3Li + CuI Cu Li+ + LiI
H3C
Gilman's reagent
(dimethylcuprate, dimethylcopper lithium)
314
Br Li CuLi
4 Li(0), ether CuI
2
2
THF
CuLi + OTs
2
CuLi THF
+ I
2
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Reaction of cuprates with aryl and vinyl halides
H H
(H3C)2CuLi double bond geometry
I CH3 is preserved
H H
Br CH2CH2CH3
(H3CH2CH2C)2CuLi
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Br Br
H R CHBr3, KOH H R
R H R H
trans-alkene trans-cyclopropane
8
14.12: An Organozinc Reagent for Cyclopropane Synthesis
Simmons-Smith Reaction
ether
CH2I2 + Zn(Cu) I-CH2-Zn-I = H2C:
carbene
H
CH2I2, Zn(Cu)
ether
H
cis-alkene cis-cyclopropane
H R CH2I2, Zn(Cu)
H R
R H ether R H
trans-alkene trans-cyclopropane
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