Introduction to New Trends in Cross-Coupling - New Trends in Cross-Coupling: Theory and Applications - page 9

1920

Job - 1924
Combined organometallic reagents
with metal catalysis

1940

Kharasch - 1943
First cross-coupling of ArMgBr
with sp 2 -Br

F irst cross-coupling
reaction

1960

Introduction of Pd
as catalyst

Heck - 1968 Pd-catalyzed coupling of sp 2 -HgCl with alkene s

Fujiwara-Moritani - 1969
Pd -catalyzed cou pli ng of sp 2 -H
with alkenes

1970

Kochi - 1971 Fe-catalyzed cou pli ng of sp 2 -MgX wi th sp

2 -B r

Introduction of
PR 3 ligands
Introduction of
alternative organometallic
coupling partners

2 -MgX

Kumada-Corriu - 1972 Ni-catalyzed coupling of sp

Cassar-Heck-Sonogashira - 1975
Pd-catalyzed coupling of sp-H
wit h sp 2 -I
Introduction of Cu co-catalyst
(Sonogashira)

with sp 2 -Cl

Mizoroki-Heck -1971-72
Pd-catalyzed coupling of sp 2 -I
with alkenes

Negishi - 1976-77 Pd-catalyzed coupling of
sp 2 -ZnCl with sp 2 -I
Kosugi-Migita-Stille - 1977-78 Pd -catalyze d coupling of
sp 2 -SnR 3 with sp 2 -Cl
Suzuki-Miyaura - 1979-81 Pd-catalyzed coupling of sp 2 -BR 3
with sp 2 -Br

1980

C(sp 2 )-alkene

C(sp)-C(sp 2 )

1990

Hiyama - 1989 Pd catalyzed coupling of sp 2 -SiR 3 with sp 2 -I

Buchwald-Hartwig - 1995
Pd -catalyzed coupling of NH with sp 2 -
Br

C(sp 2 )-C(sp 2 ) Introduction of direct

formation of C-X bonds

C-X(X=N,O,S)

Figure 1.6 Simplified time-line of events in the early development of cross-coupling reactions.