Suzuki-Miyaura Cross-Coupling Reactions
‫ڵ‬ຯਂ͍ੜ෺‫׆‬ੑΛ༗͢Δ ༗‫ػ‬Խֶతʹॏཁ
R
BY2
stereodefined organoboranes
X R'
stereodefined haloalkenes
transition metal catalyst
X M(II) R'
XA
RA
organoboraneͱhaloalkeneͰ൓Ԡ͕ਐߦ͠ͳ͍ͷ͸ɼtransmetalation͕‫ݪ‬ҼͰ͸ʁ
Miyaura, N.; Yamada, K.; Suginome, H.; Suzuki, A. J. Am. Chem. Soc. 1985, 107, 972-980
The Nobel Prize in Chemistry 2010 was awarded jointly to Richard F. Heck, Ei-ichi Negishi and Akira Suzuki
"for palladium-catalyzed cross couplings in organic synthesis".
hydroboration reaction 1973- Full Professor in the Department of Applied 1994 Chemistry, Hokkaido University
Coupling Reactions
Cross Coupling (Heterocoupling)
/nobel_prizes/chemistry/laureates/2010/index.html
Dr. Akira Suzuki
1959 Ph. D. at Hokkaido University
Postdoctoral associate with Herbert Charles 1963- Brown (Nobel laureate 1979) at Purdue University, 1965 investigating the stereochemistry of the
The Common Mechanism of Cross-Coupling
RA
X R'
transition metal catalyst
R R'
R R' redctive elimination
X R'
M(0)
oxidative addition
R M(II) R'
transmetalation
Organozinc Compounds……Negishi Coupling Organotin Compounds……Migita-Kosugi-Stille Coupling Grignard Reagents……Kumada-Tamao-Corriu Coupling
Complicated Handling Limitations of Reaction Conditions and Substrates Toxic Metal Refuses
The Common Mechanism of Cross-Coupling
R BY2 organoboranes ‫ڞ‬༗݁߹ੑɼ൓Ԡੑʹ๡͍͠
transition metal catalyst
R
R'
stereodefined conjugated alkadienes
>99%
R
H
HB(Sia)2
O HB
O
Sia (siamyl)
Miyaura, N.; Yamada, K.; Suzuki, A. Tetrahedron Lett. 1979, 36, 3437-3440 Miyaura, N.; Yamada, K.; Suginome, H.; Suzuki, A. J. Am. Chem. Soc. 1985, 107, 972-980
Suzuki-Miyaura Cross-Coupling Reaction
–The Novel Prize in Chemistry 2010–
2011,01,22 M1 Masafumi Ando
The Novel Prize in Chemistry 2010
Richard F. Heck Ei-ichi Negishi Akira Suzuki
But ҆ఆͰ͋Δ͕‫ʹނ‬ɼCoupling Reactantͱͯ͠ར༻Ͱ͖ͳ͔ͬͨɽ
Suzuki-Miyaura Cross-Coupling Reactions
‫ڵ‬ຯਂ͍ੜ෺‫׆‬ੑΛ༗͢Δ ༗‫ػ‬Խֶతʹॏཁ
R
BY2
stereodefined organoboranes
X R'
stereodefined haloalkenes
ex) Sonogashira Coupling
Pd (0) or Pd (II)
R1 X
H
R2
R1
R2
CuX, base
Homocoupling
ex) Ullmann Coupling
X R1
X R1
Cu-powder > 200 °C
R1
R1
Cross-Coupling Reactions
Cross-CouplingͰ༻͍ΒΕΔOrganometallics
R
R'
stereodefined conjugated alkadienes
Bu
O B
O
Br
Ph Pd(PPh3)4
6h
Ph
no reaction
Miyaura, N.; Yamada, K.; Suginome, H.; Suzuki, A. J. Am. Chem. Soc. 1985, 107, 972-980
͜ΕΒΛࠀ෰͢ΔͨΊɼOrganoboron Compoundsͷར༻Ͱ͖ͳ͍͔ʁ
Suzuki-Miyaura Cross-Coupling Reactions
Organoboron Compounds Readily Available Non-toxic Air- and Water-stable Easily Removable Inorganic Boron Byproduct