Jasmone 1 - ChemistforChrist

Synthesis of JASMONE
O
O
NaOH
Even easier:
O
O
O
O
Cl
soft E
O
Na O
EtOH, H
(due to Vinologous
behaviour same
conditions can be
used as for Carboxylic
acids!)
O
OEt
Me
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O
Br 2, PPh 3
(due to Vinologous
behaviour same
conditions can be
used as for Carboxylic
acids!)
MeLi
This is a electron rich
double bond and therefore
Me 2CuLi doesn't react nicely
with this molecule.
Review on conjugated addition of Organocopper reagents: Org. React. 1972, 19, 1-113
Org. React. 1992, 42, 135-631
Revisit on Organocopper reagents:
Homocuprates (Gilman reagents): Me2CuLi, Bu2CuLi
e.g. Me2CuLi, Bu2CuLi
Mixed homocuprate: RCuR'Li
Mixed homocuprates are used in order not to waste halt of the Substituent R:
R MgX + CuCl 2 R Cu + RCl + MgXCl
MeCuBuLi (Bu-Substituent is transfered),
transfered!)
R
Li
Cu R'
Heterocuprates: RCuXR'
e.g. -SPh, -OtBu (these substituents are never transfered)
R Li + CuSPh RCuSPhLi
Me
Me
OH
OEt
O
O
O
Me
Br
Br
H
Me 2CuLi
(The R substituent is transfered, alkynes are never
R3CuLi2 (higher order cuprates)
Those were discovered by following experiment: MeLi and CuI were mixed in various rations and the Me-
Singlet in the 1 H-NMR was observed: When mixing MeLi and CuI in a 3:1 ratio only a single species could be
seen.
Cyanocuprates (Lipshutz cuprates) R3CuCNLi2
2 RLi + CuCN R 2CuCNLi 2 (R 2CuLi, LiCN)
Cyanide (CN) acts as the 3rd R group in relation to the creation of higher order cuprates.