Tokyo Chemical Industries (TCI) Reagents Guide 8th Edition -Synthestic Organic Chemistry,Materials Chemistry_GH

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High reactivity but low stability
Reactive without phosphine ligands at room temperature Inexpensive and easy to remove
In many cases heating is required for the reactions to
proceed.
Formation of cationic complexes is unfavorable for metal
exchange reactions.
Effective to add some salts like LiCl for the reactions to
proceed
Only in a special case will the reactions proceed.
Use of highly active catalysts
Use of heteroaromatic chlorides (R = heteroaromatic rings)
The order of the reactivity as follows:
Electron-withdrawing group > electron-donating group
Chemically stable and easy to handle
Little by-product
Expensive and hard to remove
Improves oxidative addition
Electron-withdrawing group is effective for oxidative addition. Improves reductive elimination
R X + 3
R X +
Kumada-Tamao-Corriu cross-coupling
Ni(0) cat.
R X + R' MgX
R R'
Negishi cross-coupling
Pd(0) cat.
R X + R' ZnX
R R'
(R'–AlR 2 and R'–ZrCp 2 Cl can be also used.)
Kosugi-Migita-Stille cross-coupling
R R'
R' SnR''
Pd(0) cat.
Suzuki-Miyaura cross-coupling
R R'
R' B(OR'')
Pd(0) cat.
2
Base
Hiyama cross-coupling
R X + R' SiR'' 3
Pd(0) cat.
(SiR'' 3 =Si(OR) 3 , SiR 3-n F n , etc.)
(SiR'' 3 =Si(OH)Me 2 : Hiyama-Denmark coupling)
Sonogashira-Hagiwara cross-coupling
Ar X + R'
Pd(0) cat.
Cu(I) cat.
Base
Miyaura-Ishiyama Borylation
Ar X Pd(0) cat.
(RO) 2 B B(OR) 2 Base
+
Ar
R
R'
R'
Ar B(OR) 2
Buchwald-Hartwig cross-coupling
Chan-Lam-Evans cross-coupling
Ar X +
H YR' n
Y= N, O
Pd(0) cat.
Base
Ar
YR' n
Cu(OAc) 2
Ar B(OH) 2 + H YR' n
Ar YR' n
Base, O 2
Y= N, O, S
Mizoroki-Heck reaction
Carbonylation via CO insertion
Pd(0) cat.
R X +
R
Nu H
R'
R'
or Pd(0) cat.
Base
R X + R' M
or
CO
H
R
O
Nu
or R'
or H
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