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NO
2
I
5mol%Pd(PPh
3
)
2
Cl
2
ZnCl
+
10 mol % DIBAH, 25 °C
O
2
N
74 %
Negishi 1977
Scheme 1.8 Pd-catalyzed coupling of organozinc reagents with aryl iodides.
O
SnPh
3
0.05 mol % PdBn(PPh
3
)
2
Cl
O
Ph
+
Cl
Ph
HMPA, 60-65 °C
86 %
Stille 1978
Scheme 1.9 Pd-catalyzed coupling of organotin reagents with aroyl chlorides.
CO
2
Me
3mol%Pd(PPh
3
)
4
Br
B(OH)
2
+
Na
2
CO
3
,PhH
H
2
O, 100 °C
MeO
2
C
94 %
Suzuki 1981
Scheme 1.10 Pd-catalyzed coupling of organoboron reagents with aryl bromides.
Continuing the investigations of the use of alternative nucleophiles,
Kosugi and Migita,
41
followed by Stille,
42
reported cross-coupling reactions
involving organotin reagents (Scheme 1.9).
Extending the range of possible organometallic coupling partners, fol-
lowing the report by Murahashi's on a transmetallation strategy for using
trialkylboranes,
43
Suzuki and Miyaura disclosed their findings on the
beneficial effect of added bases in cross-coupling reactions of alkenylbor-
anes with aryl halides catalyzed by palladium (Suzuki-Miyaura reaction)
(Scheme 1.10).
44
Since Suzuki and Miyaura's seminal report, this cross-coupling reaction
has been extensively developed and its mechanism studied in great detail.
Chapter 8, authored by Alastair Lennox and Guy Lloyd-Jones, describes the
discovery, development and deployment of boron reagents in cross-coupling
reactions, including mechanistic analysis. In Chapter 11, the topic of
stereospecific and stereoselective Suzuki-Miyaura coupling reactions is
discussed by Ben Glasspoole, Eric Keske and Cathleen Crudden.
Subsequent to the introduction of organoboron reagents as cross-coupling
partners, Hiyama reported ecient cross-coupling reactions of arylsilanes by
the use of fluoride additives (Scheme 1.11).
45
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