Baran Group Meeting
Sept. 11, 2010
Dane Holte
1990–1997
Scope of the journal (from ACS website):
Organometallics publishes original contributions on fundamental studies of
all aspects of organometallic chemistry.
–synthesis of organometallic compounds
–structure and bonding (experimental and theoretical studies)
–chemical reactivity and reaction mechanisms of the metal-carbon bond
as well as of other organic and inorganic functionalities present in the
molecule
–applications: organometallic reagents in organic, inorganic, and
polymer synthesis
–catalytic processes in which an organometallic compound is the
precatalyst or catalyst or in which organometallic species are intermediates
–applications of organometallic compounds in the synthetic aspects of
materials science and solid-state chemistry
–bioorganometallic and environmental organometallic
chemistry.
Titanium
H
HO
Br
Br
Me
Me
Me
Me
TiCl2 Me
TiCl2
Me
Me
Me
Br
Me
Me
TiCl2
ArO
Ph
Et
Ph
Ph
Et
Ti
(ArO)2TiO
100 ºC
Ph
Et
H2O
Et
ArO
Ti
2. 12 M HCl
Et
Ph
ArO
1. n-BuLi (2 eq.),
then TiCl3•3THF,
-40→reflux
1993,12, 2248–2257.
Ph
ArO
2 Na
Cl
ArO
Cl Et
Et ArO
Et
Et
Ti
Et
Et
or
Et
Et
I2
I
Et
Et
Br
Et
Et
Et
Et Ph Ph
Cl
Mg then,
Et
TiCp2
Et
OH
Et
Et
Me
Et
PhCN
Ph2CO
Et
I
Most cited article: Safe and convenient procedure for solvent purification,
Grubbs et al., 1996, 15, 1518–1520.
H
named reaction?
mechanism?
Me
Et
Two papers I won't talk about (for those interested in lasers):
1. Laser-induced explosive decomposition of (fluoromethyl)silanes:
reductive chemistry initiated by laser photolysis, 1993, 12, 171–176.
2. The germanium-hydrogen bond dissociation energies of
organogermanes. A laser-induced photoacoustic study, 1991, 10, 746–750.
Br
Me
Relatively "young," existing only from 1982
through the present
ISI Impact factor: 3.83
(falls between JACS 8.58 and Tet.
Lett. - 2.54 to give you an idea...)
Whats been left out of my presentation?
-almost everything (39834 pgs. 1990–1997)
-Palladium
-Metathesis
-talk is generally tailored to our lab and my
interests (see lasers - below)
MeLi,
-78 ºC
H
OH
Me
Cl2EtAl
Cp2
N
Ph
1993,12, 2911–2924.
Cl
Ti
Me
Me
1. -AlCl2Et
Cp2TiCl2
EtAlCl2
2. HCl
Me
associated name? 1990,9, 3022–3025. rationalize diastereoselectivity?
Baran Group Meeting
Sept. 11, 2010
OMe Cp
Li
MeO
TiCp2
Cp2TiMeCl,
Tantalum
Ti Cp
C2H4
Ph
Ta(DIPP)3Cl2•OEt2
then 80 ºC
OMe
Cp
Cp Ti O
Dane Holte
1990–1997
Cp
Cp Ti N
O
p-BrC6H4CN
Na/Hg
Ph
O
Cp Cp
Zr
n = 1, 3
1. CO
( )n
OMe
1. t-BuNC
2. I2
N
MeO
I
R
I
I
MeO
SCl2
Nt-Bu
MeO
Ph
iPr
(HPPID)3Ta
O O
Et
Me
H
O
2. MeOH
Ph
Ph
Zirconium and Hafnium
OMe then Δ
O
MeO
1993,12, 4182–4187.
( )n R
(PPID)3Ta
Ph
DIPP = iPr
ZrCp2
(PPID)3Ta
Ph
O
S
OMe
O
iPr
Me
RCN
mechanism?
CO2Me
Et
OH
Meyers and
OH
O
OH
OH
OMe
1991, 10, 2921–2930.
Me
Ph
Me
1992, 11, 1981–1983.
COMe
Higashiyama
Me
Cl Hf N
N
N
R
Me
5 steps
aklavinone
N
Cl Hf N
iPr
H
OMe
CO2Me
Et
OH
Cl Hf N
N
O
Me
Et
C(SMe)3
1. LiC(SMe)3
2. MeI, HMPA
3. PPh3
Cr(CO)3
55%
Cr(CO)6
O
Me
Ph
O
The only (formal) total synthesis you'll see in this presentation: aklavinone.
1991,10, 537–539.
Me
Ph
Chromium and Molybdenum
(For more on Fischer carbene-type reactivity see Ke Chen's 2007 GM)
77 %
iPr
Ph
1990, 9, 266–273.
OMe
N
Cl Hf N
iPr
Ph
named reaction?
Br
Cp ZrMeCl,
Li 2
-78 ºC,
Ph
O
(PPID)3Ta
Ph
Ph
HO
Mo(CO)6, Bu3SnOTf Ph
NEt3, Et2O
mechanism?
O
SnBu3
65%
1995, 14, 3628–3629.
Baran Group Meeting
Sept. 11, 2010
Me
Me
TFAO
CO
Mo
N
CO
N
Me
CO
OC
Mo CO
N
CO
N
Mo(CO)6
A
B
nuc
nuc, PhMe
B (5 mol%)
HO2C
Ph
O
2. TMEDA
nuc, PhMe
OAc
Cl
OH 1. WOCl
4
Me
O
W
C (5 mol%)
Cl
O
nuc
Pr
Ph
O
Pr
nuc
Me
Me
Ph
Me
Me
Me
WCl2(PMePh2)4 H2O
CO2Me
O
Re
O
O
O
R
R
R
O Re
O O
R
O Re
O O
Cp*ReO3
HO
O Re
O O
R
R
D
O
D
+
D
D
L L
O
W
L
O
Ln
LnW
D
D
D
D
D
O
O
D
D
D
D
cc
Ln W
D
W
D
R
D
O L
D
CD2 +
Cl W
CD2
L Cl
WCl2(PMePh2)4
+
1995, 14, 3138–3140.
CO2Me
D L
D
O
Me
O
D
D
O
O
Re
Hammett studies
and molecular orbital
calculations add
evidence to the
formation of a
rhenaoxetane during
the course of the
reaction (J. Am.
Chem. Soc. 1996,
118, 2625–2633).
Me
1990, 9, 3026–3027.
WCl2(PMePh2)4 H2O
Re
O
Ph
O
O
Me Me
O
A rare example (as of 1994) of a isolable rhenium
Ph oxo-alkylidine which is capable of olefin metathesis
OR
(GaCl3 cocatalyzed) Characterized by x-ray.
OR
1994, 13, 2728–2732.
R = CO(CF3)2Me
O
Pr
1997, 16, 942–950.
Me
OAc
Pr
Ph
RO O
THF Re
C
nuc, PhMe
A (5 mol%)
Pr
Dane Holte
1990–1997
D
D D
1992, 11, 3965–3970.
(Co)5ReBr + PPh3
CO
CO
PPh3
PPh3
CHCl3 OC
CO Na/Hg OC
Re
Re CO Na + TfO
OC
Br
OC
Δ
O
OEt
THF, -78 ºC
Dane's note:
You can make an
enolate out of
anything.
1990, 9, 453–466.
PPh3
OC
N
Re
OC
O
PPh3
Et
Me
OEt
CN
PPh3
CO
OC
CO
OC Re
Ph3P
O
OEt
Baran Group Meeting
Sept. 11, 2010
Iron and Ruthenium
I
Fe
I
OMe
TMS,
(Ph3P)2PdCl2,
Cu(OAC)2•H2O,
iPr2NH, 85 ºC
TMS
Fe
TMS
OC
Fe Fe
KOH, H2O
MeOH
Cp
CO
Cp
AgPF6, RX
CH2Cl2
Cobalt and Rhodium
( )n
R
Co2(CO)8,
O
HSiR3, CO AcO
OMe
Fe
OC
O
Fe CO
PF6
X
R
nuc
OC
rt, 50–95% yield, 4 mol% cat.
R
O
( )n+1
mechanism?
OSiR3
1991, 10, 21–23.
n = 1–3
1992, 11, 2757–2759.
O
Cp
Dane Holte
1990–1997
O
Cp
O
Fe CO + nuc–R
X
O
1990, 9, 745–755.
AOT
Me
Ph
Ph
P
SO3Na
P
Me
O
ClO4
Rh
Ph
Ph
N
Ph
Ph
Me
cat.
imine
SO3Na
RSO3Na
Fe
TPPTS=
[45](1,2,3,4,5)Ferrocenophane
or [4]Superferrocenophane
1990, 9, 497–503.
RuCl3, TPPTS
HCO2Na, H2
R1
R2
OH
>90% yield
none
0.1 M AOT
0.01 M N(nBu)4I
P
SO3Na
R2
O >90% yield
0
0.1
0
R1
R2
O
"RuX"
[Ru]
O
+
Ph
CO2Et Ph
40% ee
(1R, 2R)
1994, 13, 745–747.
[Cp*Ru(OMe)]2
CF3SO3H
HO
>99
>99
>99
"Cu"
mechanism?
HO
RuCp*
1993, 12, 955–957.
time (h)
ee (%)
4
95
19
59 (R)
86 (R)
80 (S)
1996, 15, 3161–3169.
Chem. Rev. 1995, 95, 849–864.
Angew. Chem. Int. Ed. 1994, 33, 2197–2199.
1991, 10, 2126–2133.
OH
yield (%)
Reverse micelles form in situ, but 15-crown-5 is
used to break apart the aggregates. Maximum
ee is achieved when sulfate anion can
coordinate with cationic rhodium species.
SO3Na
[RhCl(COD)2]2
TPPTS, H2
R1
[15-crown-5] (M)
CO2Et
+
N2
41% ee
(1R, 2S)
iPr
N N
N Cu
E
N N
H
iPr
"Rh"
Ph + EtO
Me
N
N
N
Ph
85% ee
(1S, 2S)
Me
N
N
CO2Et Ph
N N
L
N Rh
L
N N
R
R
1995, 14, 2148–2150.
CO2Et
82% ee
(1S, 2R)
tBu
E
H
tBu
Baran Group Meeting
Sept. 11, 2010
Pt+ + H2O2
AgSbF6 Me
Me
Me
Ir PMe
3 DCM, rt
Me
I
Me
Me
Me
Me
Me
Et
Et
Br
CO2H
Ph
as above
Ph
Me
O
CO2H
1991, 10, 804–807.
OTMS
O
Ni(acac)2, PPh3
Et
<5% Wurtz pdt.
R
1990, 9, 3053–3064.
O
OH
Ph3PAuNO3 R
R
O
AuPPh3 Δ
R
+ CO2 + Au
R
R
Me
H
NiLnCl
Et
Et
~70%
O
[(PPh3)Au]3OBF4 +
N2
TMS
1995, 14, 5015–5016.
PdCl2(PPh3)2
+
H
O
mechanism?
OH
O
1993, 12, 3553–3560.
OH
OH
N
N
Na2PdCl4
Pd
tBu
(esoteric?) named
reaction?
Ph
Cl
Cl
Ph
Ph3PAu
AuPPh3
OH
I
Cl
Zn, H2O
tBu
Pd
Ph3PAu C AuPHPh3BF4
characterized by x-ray
crystallography
1995, 14, 4969–4971.
Zn, NEt3, THF, 60 ºC
I
Ph
Cu(CN)ZnCl 90% desired
1991, 10, 2178–2183.
Et
Me
Et
OTMS
TMSCl, Me2Zn
tBu
ZnBr + 22% Wurtz pdt.
2. CuCN•2LiCl
-30 ºC
CO2H
88% (89:11, E:Z)
Et
1. Zn, THF,
0 ºC
Cl
HO Me
1991, 10, 623–631.
1993, 12, 148–156.
1994, 13, 3442–3451.
1995, 14, 1161–1167.
Adv. Synth. Cat. 2007, 349, 797–801
THF, 0 ºC
Et
1990, 9, 284–286.
58%
Many publications by G. Strukul:
Zn
1994, 13, 2548–2550.
Me
CTAB, 5 N NaOH, CO
PtOOH + H+
-catalytic in Pt
-can be rendered asymmetric
-baeyer-villiger and epoxidations
-modest ee and yields
-CH4
Ir PMe
3
Me
Ni(CN)2•4H2O, PhMe
Et
Me
Ir PMe
3
Me
Me
Ir H
PMe3
Dane Holte
1990–1997
N
OH
1992, 11, 2750–2752.
same reaction does
not proceed in
organic solvent
Cl
Zn, H3O+
95%
-OH
O
1990, 9, 2649–2650.
95% (mixture of cis/ trans)
Baran Group Meeting
Sept. 11, 2010
Dane Holte
1990–1997
Ph
TMS
B Cl + N
HO
B N
DCM
1
R
B
Na2CO3 • 1.5H2O2
R
3
THF/H2O, 50 ºC
Sodium percarbonate is used to oxidize organoboranes in this paper.
However, a quick search reveals it is a general source of (anhydrous)
H2O2. Additionally, it is a "stable and easily handled reagent that has
excellent shelf life."
1990, 9, 1316–1320.
Tetrahedron 1995, 51, 6145–6166.
OTBS
CH2O2Me
OTBS
Me
OMe , TMEDA
H
O
H2
O
Me
O
R1OH + R2OH + R3OH
LiAl(OC(Ph)(CF3)2)4 +
CO2Me
1997, 16, 1501–1502.
R2
LiAlH4
CF3
CF3
LiAl(OC(Ph)(CF3)2)4 O
toluene, 94%
OMe
Me
H
O
OMe
Me
Exclusively 1,4 addition utilizing soluble aluminate catalyst. Must use toluene.
1996,15, 3776–3778.
N(iPr)2
Ph
Ph
Ph
Ph
B
Ph
Me
Ph
B
GaCl4
Ph
Me
1995, 9, 3762–3767.
1990, 9, 2342–2349.
"Genuine Heterocycles"
Se
tBu
O
LDA
+ Cl
R B
O
THF, -78 ºC
Cl
R O
B
O
→ rt
Li
R
B
O
THF, rt
N
tBu
16%
tBu GaCl
3
Me
Me
N
Si
N
P
tBu
Se Me
1992, 11, 2241–2250.
O
O
R
P
GaCl3
TMS
B
18 h
H2, 5% Pd/C
N
O
R
PhMe 24-36 h
110 ºC
O
N(iPr)2
P
GaCl3 characterizable
CH2Cl2
white solid crashes
pentanes
PhH out of solution
mechanism?
Ph
rt, then 110 ºC
mechanism?
Ph
(iPr)2N
(iPr)2N P Cl
Ph
Ph
CO2Me
B
O
1992, 11, 1948–1954.
Cl(SiMe2)4Cl
+
THF
Me2Si
Me2Si
SiMe2
SiMe2
hν,
Me2Si
Me2Si
SiMe2
SiMe
2
hexane
Si
20 %
Me2
First cyclic acetylene. Stable in PhMe at 110 ºC. Reacts as you would imagine.
1992, 11, 1009–1011.
BrMg
MgBr 52 %
Baran Group Meeting
Sept. 11, 2010
F3C
TMEDA
OH
F3C CF
3
F3C CF
3
CF3 1. n-BuLi,
O
Ge
2. GeCl4
3. MeOTf
O
Me Me
Me
Ge Bu NEt4
O
O
Ph
Se
Pr
As
+
PhH
Ph
80 ºC
20 h
complete regio- an stereoselectivity
Ph
TMS
Cp*2La
Me
TMS
Et
-CH2(TMS)2
Et
H
Et
Me
Me
OH
(68:32)
Unprecedented for
lanthanides (known for
groups 1, 2, 12, and 13).
Cp*2La
Me
2.0 catalytic
turnovers / day
(50 ºC)
Me Me
OH
93 % Ph
1995, 14, 4975–4976.
2.3:1 ratio of
regioisomers
Me
Et
Cp2*La
1990, 9, 3015–3019.
Et
OTs
Me
Me
Et
OTs
Me3Sn
Me3Sn
Me3Sn
Me3Sn
(Cp*2SmH)2 +
Cp*
N
Cp*
N
"In the 1H NMR spectrum, the presence of H2 (δ 4.46) [...]"
1996, 15, 3913–3915.
SnH4
Stannane: boils at -52.5 ºC, toxic, ignites
in air. Also, a capable reducing agent.
"a more violent explosion and fire resulted. [...] In spite of this upset, we
were able to work up the reaction mass and isolated hexa-n-propyltin, as
the only product, in 89% yield."
1993, 12, 3015–3018.
1995, 14, 1450–1452.
exclusively orthometallation, no imine
hydrogenation
(observed with Ti)
Sm
double hyperconjugation in the δ tin effect
1993, 12, 697–703.
LiAlH4 + SnCl4
Et
1990, 9, 1508–1510.
homohyperconjugation in the γ tin effect
Me3Sn
+ regioisomer
Cp2*La
The γ and δ Effects of Tin.
Me3Sn
Et
Et
Me
Me Me
AsPh2
Se
Pr
F3C CF3
Germanium geometry
significantly distorted
from ideal tetrahedral,
but "strain release" upon
coordination to carbonyl
CHO
O
O
1. BuLi
2. Et4NBr
F3C CF3
DCM, rt,
Dane Holte
1990–1997
OC
U
CpCo(CO)2
P Ph
Me
Me
U O
Co
P
Ph
Me Me
1990, 9, 1141–1146.
1982-1988
1989-1995
1996-2002
tiv
ac
n
io
at
s
si
he
at
et
m
C
N
H
*
bd
ol
m
*
tin
*
st
od
rh
el
H
g
ng
tu
*/
ck
ni
*
en
rh
lt
ba
*
an
tit
*
en
th
r*
er
/f
co
er
cu
m
C
-H
2003-2009
ru
n
iro
d*
d*
iri
na
i*
m
os
*
ur
/a
va
ld
go
*
lv
si
*
d*
ob
ni
lla
pa
-H
C
s
n
io
at
tiv
ac
si
he
at
et
m
C
H
N
*
ol
bd
d*
tin
rh
o
m
g
t*
H
el
gs
tu
n
*/
er
cu
m
ni
ck
n*
rh
e
lt
ba
co
tit
an
*
n*
er
r*
/f
ru
th
e
iro
n
*
iri
d
*
i*
m
os
*
ur
*
/a
va
na
d
ld
go
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lv
*
ob
ni
d*
lla
pa
Total papers published, by title keyword
500
375
250
125
0
Papers, normalized for growth of
journal, by title keyword
0.020
0.015
0.010
0.005
0