short literature - cpb-us-e1.wpmucdn.com · 11/11/2011 · 60 °c 20 °c 280 nm 280 nm 380 nm 380...
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Short Literature11/15/10
Dustin Raup
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Prof. Ben Feringa
- PhD in 1978 with Prof. Hans Wynberg (Univ. of Groningen)- Research Scientist with Royal Dutch Shell (1978-1984)- Lecturer in Organic Chemistry, Univ. of Groningen (1984-1988)- Prof. of Organic Chemistry (1988-present)- Department Chair (1991-1995)- Director Stratingh Institute for Chemistry (2003-present)- J. H. vanʼt Hoff Distinguished Prof. (2003-present)- Academy Professor, Royal Netherlands Acad. of Sciences- Editor of Organic & Biomolecular Chemistry
Research Focus:
Asymmetric CatalysisChirality
Biomimetic and Catalytic OxidationOrganogels and Smart MaterialsMolecular Switches and Motors
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Molecular Motors
Inspiration from Nature
Bacterial flagellum translate molecular motion to do locomotive work!
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Molecular Motor Applications
Controlling the properties of liquid crystal films
S
S
S
S
hvMe
Me
Me
Me
Molecular “brakes” or Switches
Fast Propellers for microfluidics
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Unidirectional Light-Driven Molecular Motors
Me Me
Me Me
Me
Me
Me
Me
20 °C60 °C
280 nm
280 nm
380 nm
380 nm
Nature, 1999, 401, 152-155
First Report of Continuous Unimolecular Motion by Feringa
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Synthesis of the New System
SH 1. NEt3, toluene, 50 °C
OO O
2. AlCl3, 0 - 22 °C
67% over 2 steps
S
O
OH
O 1. EDC, HOBT, NHNMe2, DIPEACH2Cl2, rt, 83%
2. NHNH2, EtOH55%
S
N
NMe2
O
NH2
I OAcOAc
S
N
NMe2
O
N
S
S
DMF -50 to 22 °C55%
SNMe2
O
S
S
SNMe2
O
S
PPh3, 80 °C
92%
Barton-Kellogg Diazo-thioketone coupling
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Schematic of How the Bidirectional System Works
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How The New System Works
S
S
O
NMe
Me S
S
O
NMe
MeS
S
O
NMe
Me S
S
O
NMe
Me
S
S
O
NMe
Me S
S
O
NMe
MeS
S
O
NMe
Me S
S
O
NMe
Me
hv hv
hvhv
base
base
heatheatheatheat
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The Pauson-Khand Reaction
- Cobalt alkyne complex first reported in 1971, by Pauson and Khand, reaction run but uncharacterized.- Complex first intercepted and characterized by Nicholas in the Nicholas Reaction- Formal [2+2+1] cycloaddition of alkyne, alkene and CO reported by Pauson and Khand in 1973.
R1 R2
R3
COCo2(CO)6 R1
R1
R1
O
R1OH
Co2(CO)6
then oxidantR1
Nuc
R2
R2NucH
Pauson-Khand
Nicholas
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Mechanism
(CO)3Co Co(CO)3
R1 R2
(CO)3Co Co(CO)3R1 R2 Co(CO)3
Co(CO)3
R1
R2
-COCo(CO)3Co(CO)2
R1
R2
R3Co(CO)3Co(CO)2
R1
R2
R3
Co(CO)3Co(CO)3
R1
R2
+CO
+CO
R3
Co(CO)3Co(CO)3
R1
R2
OR3OR3
R2
R1Co(CO)3Co(CO)3
OR3
R2
R1
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Visible Light Activated Pauson-Khand
HH R
H
O
R
XS
1 atm COCo2(CO)6
22 °C
halogen lampor sunlight
HH
O
ferrocene
HH
O
TMS
78% 78%
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Using Light for Activation?
Prior Art
HH R
H
O
R
XS
1 atm COCo2(CO)6
22 °C
halogen lampor sunlight
HH R
H
O
R
XS
1 atm COCo2(CO)6
22 °C
halogen lampor sunlight
- Alkyne-Co complex undergoes homolytic bond cleavage in light and radicals
- Suggests that light facilitates loss of CO ligand (RDS as as suggested by Magnus and coworkers)
TEMPO22 °C
300 nm hvheat
37-99% yield
Org. Lett., 2005, 7 (14), pp 3033–3036
up to 95% yield