R.A. Rodriguez Leo Armand Paquette Baran GM 2011-08-20 ...
R.A. Rodriguez
Born in Worcester, Mass., July 15, 1934
1390 publications (111 reviews)
42 patents
17 books
38 book chapters
Research interests
Heterocyclic chemistry
Hydrocarbon chemistry
Natural product synthesis
Synthetic methodology
Catalytic asymmetric methods
Organoetallic chemistry
Organosulfur reagents
Leo Armand Paquette
B.S., Holy Cross College, 1956
Ph.D., MIT, 1959 synthesis of azasteroids
and regioselectivity in Baeyer-Villiger
(Adv. Norman A. Nelson)
Upjohn, medicinal chemist, 1959-63
Prof. Ohio State University, 1969-present
Honors and Awards
1965 Alfred P. Sloan Fellow
1971 Morley Medalist Cleveland Section
1976 Guggenheim Fellow
1979 Columbus Section Award
1980 Senior Research Award, OSU
1981 Kimberly Professorship in Chemsitry
1987 Arthur C. Cope Scholar
1984 National Award for Creative Work
in Synthetic Organic Chemistry
1989 Senior Humboldt Fellow
1990 Sullivant Medal, OSU highest honor
1992 Awardee of the Japanese Society for
the Promotion of Science
1992 Ernest Guenther Award
2002 S.T. Li Prize Science and Technology
Syntheses Discussed
[4]peristylane
Elassovalene
OH
Dodecahedron
[22](1,5)Cycloctatetraenophane
Me
Me
H
O H H Me
Me
Me
Me
Me
Me
Pentalene
Me
OAc
Me
Me
Me Salsolene oxide
4a¦Â, 10¦Â-doladiol acetate
Me
HO
Me
Me
O
O
Me
O
Me
Me
O
MeO
Me
O
O
OMe
Me
H
HO 3
C(3) OH ¦Á; C(3) OH ¦Â
(-)-Austalide B
Timeline: Career in review
Natural Product Synthesis 1979-present
Gymnomitrol and Isocomene 1979
55 total syntheses to date
Hydrocarbons 1974-1990
Dodecahedrane 1982
Heterocyclic chemsitry
1962-1975
Azepine 1962
Oxy-Cope RR 1978-2000
Ag(I) cat. RR di-¦Ð?methane RR
1975-1984
1970-75
Postdoctoral Researchers
from the Paquette group:
Steven Ley (1972-1974)
Louis Barriault (1997-1999)
(-)-polycarvernoside A
Baran GM
2011-08-20
1962
1968
1975
Organosulfur 1964-74
¦Á-Halosulfones 1964
1981
Squarate esters Indium reagents
1993-97 1995-2000
1987
1993
2000
Silicon chemistry
Polyspiro tetrahydrofurans
1977-1984
1981-2004
2006
2011
Leo Armand Paquette
R.A. Rodriguez
Heterocyclic and Carbocycle Chemistry 1962-1975
Upjohn and OSU
Syntheses and derivatives:
N
H
Azepine
Baran GM
2011-08-20
MeO
N
N
Syntheses and derivatives:
JACS 1962, 84, 4987
JACS 1963, 85, 4053
JACS 1964, 86, 4092
JACS 1964, 86, 4096
JACS 1965, 87, 1718
JACS 1965, 87, 3417
JACS 1968, 90, 6148
JACS 1972, 94, 6751
O
Oxepin
MeO
Azabullvalene
1967
Azasemibullvalene
1969
Bullvalene
Semibullvalene
e.g. phenol and chloramine
A Synthetic Entry into the Azasemibullvalene System
Photochemistry of Carbocycles
O
O
Me
H
hv
hv
H
1/4 products
acyclic
¦Á,¦Â-cyclopropane
ester
Me
Me
Me
O
Me
Me
ClO2SN
Me
C O
Me
Me
Me O
O
JACS 1969, 91, 7108
ClO2SN
Me
Me
The Protonation of Hexamethyl Dewar Benzene and Hexamethylprismane
in FSO3H?SbF5?SO2 "magic acid"
Me
Me
Me
HN
Me NaOH Me
Me
Me
1.
Me
Me
Me
Me
Me
Me
JACS 1968, 90, 7147
Me
Me 2. K2CO3
Protonation of cis-Bicyclo[6.1.0]nona-2,4,6-trienes in superacidic media
H
?95 ¡ãC
H
JACS 1973, 95, 3386
Me
Me
Me
Me
Me
Me
N
MeO
Novel aromatics 1976
The First 8C-6¦Ð Huckeloid System:
1,3,5,7- Tetramethylcyclooctatetraene Dication
Me
FSO3H?SO2ClF
Me
Me
Me
Me3O+BF4-
JACS 1969, 91, 6107; JACS 1967, 89, 5480;
JACS 1975, 97, 6124; JACS 1970, 92, 4338
Me
Me
Me
O
Identification of cationic species 1968 (collaboration with Olah)
Me
Me
trans-Bicyclo[6.1.0]nonan-2-ones
2,3 Homotropone
JACS 1967, 89, 5633
Me
Me
Me
NSO2Cl
Me
Me
Me
ClO2SN
+
initial trans cation
JACS 1976, 98, 1267
Me
2+
Me
Me
Me
+
+
Me
Me
Me
Me
JACS 1976, 98, 4327 Bis(tetramethylhomocyclopropenyl) Dication
Leo Armand Paquette
R.A. Rodriguez
Synthetic Methods:
1. Ramberg-Backlund 1964-74
Baran GM
2011-08-20
3. di-¦Ð-methane RR 1975-80
Upjohn: Conversion of Mercaptans to Homologous Terminal Olefins
1989 [3]peristylane
HO
O
[O]
SH
SCH2Cl
90%
SO2CH2Cl
97%
4. Silanes 1977-84
- cyclopentanone synthesis
Cl
S
O
S
O
O
O
Me
O
HO
X
SO2CH2Cl
base
Cl
R
S
-HCl
O
JACS 1967, 89, 4487
O
TMS
+
base
-SO2
-HCl
Me
Me
Me
Me
Me
Me
Me
Me
Me
¦Á?Vetispirene
Tet.Lett 1982, 23, 3227
Ag
Ag
Ag
H
(AgBF4)
vs >150 ¡ãC w/o Ag (I)
Br
Br
H
Me
TMS
2. Ag I cat. RR 1970-75
Ag+
O
Me
SnCl4
TMS
TMS
Me
O
Me
R
AlCl3
Cl
Me
Me
JOC 1980, 45, 3017
Chem. Rev. 1986, 86, 733
(silyl cylopropanes)
RR of ¦Á,¦Á-Dichloromethyl Sulfones
CH2SO2CHCl2
O
Me
2. nBuLi
3. TMSCl
O
JACS 1964, 86, 4383
R
1. PhSO2NHNH2
O
oxydi-¦Ð-methane
Tetrahedron 1989, 45, 3099
OH-
OH
hv
Diels-Alder equivalents
Phenyl Vinyl Sulfoxide as
Acetylene Equivalent
trans-1-(Phenylsulfonyl)-2-(TMS)ethylene as
Ethylene Equivalent
H
O
SO2Ph
H
H
H
H
PhS
MeLi
80%
JACS 1971, 93, 1288; JACS 1980, 102, 637
Ag+
(AgBF4)
40 ¡ãC
H
via ene-type
quant. clean
non-conjugated triene
JACS 1978, 100, 1597
? Indium 1995
? Zr 2002
TMS
* cis found to be less reactive
JACS 1980, 102, 4976
Leo Armand Paquette
R.A. Rodriguez
Baran GM
2011-08-20
Men of learning in ancient Greece took especial concern for "the putting together of cosmic figures.' their regular polyhedra whose mathematical elegance inspired
considerable wonder. The heritage of that wonder inevitably passed into the realm of synthetic organic chemistry and attracted the practitioners of this science to
apply their skills to the construction from carbon and hydrogen of such strained molecules...
A journey to dodecahedron: selected syntheses of hydrocarbons
[4] peristylane
octahedrane
[8 faces]
decahedrane
[10 faces]
top view
[5] peristylane
Eaton and Muller
dodecahedrane
[12 faces]
X
Tetrahedron, 1989, 45, 3099
[3] peristylane
"triaxane"
JACS, 1983, 105, 4113
[4] peristylane
top view
R
R
1. SeO2 H
2. Al2O3,
quinoline
H
1. BF3,
Et3SiH
I
[3+2]
N
wurtz
O
CO2H
Cl
O
80%
2.
CO2H
Br
S
I
O
Ts
O O
O
OH
TsOH
63% 2 steps
O MsCl/TEA 0 ¡ãC;
rt NO GOOD!!
85%
H
H
Cl
10%aq
MeOH
95%
O
O
quant [5 gram] 1. hv
76% 2. H+,¦¤
O
I 1. sulfene
N NHTs
N
SOCl2
Cl
O
O
O
HO
OH
H
HIO4,
Me
HO2C
1.
N
NaK-alloy
54% wurtz-type
¦¤
O
Ts
77%
O
O
TS
hv
quant
acetone
3.H3O+
69% 3 steps
NaOEt,
EtONO
OH
2. I2, PPh3
N NHTs
1.eth.gly., H+
2. Li, EtNH2
Hypostrophene
1. hv
¦¤
O
N OH
Several years later, Garratt and White noted that the top row (vide supra)
hydrocarbons constitutes a series of compounds characterized by the
interconnection of a smaller n-memberd ring to one twice the original size at
alternate carbons of the latter and the community decided to generalize the
Eaton nomenclature.
O
O
98%
2 steps
Ts
2. TsCl, py
3. LAH, ¦¤
64% 3 steps
After successful preparation of one of these hydrocarbons, Eaton named it
"peristylane" after a Greek word hat alludes to the similarity to "a group of
columns arranged about an open space in a manner designed to support a roof".
I
mCPBA
PhH, ¦¤
Ts
It was initially named "triaxane" in an effort to capture the C3v symmetry of its
tetracyclic framework and to depict that the cyclopropane ring rests on three
axial pillars fixed to a cyclohexane chair.
OH
O
H
When first synthesized, trixane was viewed predominantly as a chemical curiosity.
[3] peristylane
"triaxane"
? molecular modeling shows
serious nonbonded steric strain
H
I
Tet. Lett., 1974, 17, 1615
2. NaI
90%
OH LAH
O
84%
HO
O
O
Leo Armand Paquette
R.A. Rodriguez
Baran GM
2011-08-20
B
JACS, 1990, 112, 1258; Tetrahedron, 1981, 37, 4521
Br
A
B
Br
A
45 ¡ã
E
[22](1,5)Cyclooctatetraenophane
The Weiss-Cook reaction:
E
E
R
+
O
2 equiv
O
O
E
aq. buffer
O
R
E
E
2 equiv
O
1.LAH
2.NaH,
CS2, MeI;
¦¤
O
70%
1.
O
O
R
2. HCl, ¦¤
85%
- 4CO2
O
HCl, ¦¤
92%
E
O
HO
O
Br
3.Ph3PBr2
66% 3 steps
ether, rt
two-fold
Br cation-olefin
cyclization
CO2Me
1. OsO4
2.HO
OH
TsOH
OH 1.LAH
2.NaH, CS2
MeI; ¦¤
SiO2
(10X weight)
1.LAH
2. DHP/H+
83%
83%
Me
Me
O
O
H
H
Br
AgClO4
H
Br
H
PhH/pentane
Br
Br
Bu3SnH
3.TsOH
56%
69%
O
A
B
O
minor
Br
+
(~ 1:2)
major
B
Ni(CO)4
DMF
34%
Br 2 steps
all mixtures
O
all mixtures
NBS 4 eq
AIBN/CCl4
CO2Me
E
(COCl)2,
DMSO
2 eq E
E
O
E
all mixtures
Br
O
cis-bicyclo[3.3.0]
octanedione
O
85%
O
- 4CO2
E
pH = 5.6
+
E
Br
R
E
O
R
O
E
O
E
R
[3,3]
H2, Pt
EtOAc
500 ¡ãC
40%
brsm
bicyclo
[3.2.1]octane
A
JACS, 1979, 101, 4773
bicyclo
[2.2.2]octane
................
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