Baran Group Meeting
JACS: 1986 Year in Review
Selected Publishing Statistics for JACS 1986:
Will Gutekunst
Syntheses Partially or Fully Discussed
HO
Total number of papers: 1843
Total synthesis papers: 51
O
H
O
Leo A. Paquette
14 (1 total synthesis)
Barry M. Trost
6 (2 total synthesis)
Herbert C. Brown
4 (0 total synthesis)
Samuel Danishefsky 4 (1 total synthesis)
Gilbert Stork
4 (0 total synthesis)
Amos B. Smith
4 (4 total synthesis)
David Evans
4 (2 total synthesis)
Larry Overman
3 (0 total synthesis)
K.C. Nicolaou
3 (0 total synthesis)
E.J. Corey
2 (0 total synthesis)
Paul Wender
1 (0 total synthesis)
OMe
MeO
O
O
O
O
HO
NMe
MeO
(–)-grandiosol
(±)-O-methylpallidinine
compactin
HO
O
H
OH
O
HO
O
Manzamine A isolated
OH
MeO
Ryuichi Sakai, Tatsuo Higa, Charles W Jefford, Gerald Bernardinelli; 6404-6405.
mycophenolic acid
HO
(-)-punctatin A
Silphiperfol-6-ene
O
OMe
Concerted!
O
OH
H
O
O
H
O
O
O
K.N. Houk, Yi-Tsong Lin, Frank K. Brown; 554-556.
O
pentalene
allamandin
Protomycinolide IV
O
OH
CN
O
HO
MeO
NH
N
NMe
Me
O
O
HO2C
OH
H
N
HO2C
jatropholone A
O
cyanocycline
N
O
O
O
OH
Octosyl Acid
HO
O
H H
Brevetoxin A Elucidated
Yuzuru Shimizu, Hong Nong Chou, Hideo Bando, Gregory Van Duyne, Jon Clardy; 514-515
HO
H
(±)-Δ
(9,12)
-capnellene
H
CO2H
O
H
OH
(–)-coriolin
pentalenic acid
JACS: 1986 Year in Review
Baran Group Meeting
Total Synthesis of Mycophenolic Acid
Rick L. Danhesier, Stephen K. Gee, Joseph J. Perez; 806-810.
1) NaBH4, EtOH
2) TBSCl, DMAP, TEA
CHO
OTBS
OAc 3) K2CO3, MeOH
MeO
Polyene Cyclization Strategy in the Stereospecific Synthesis of B/C-trans-Morphinan. A
Total Synthesis of (±)-O-Methylpallidinine.
Shinzo Kano, Tsutomu Yokomatsu, Hajime Nemoto, Shiroshi Shibuya; 6746-6748.
OTBS
n-BuLi, MsCl
Li2CuCl4
OH
O
OMe
MgBr
MeO
PhS
MeO
LiCH2OMOM
-78ºC, THF
O
O
+
O
OEt then, HCl workup
OEt
Sealed Tube
Benzene
120o C, 14 hrs
73 %
mechanism?
OMOM
81%
HO
OH
TBSO
O
O
MeO
OH
1) Br2, t-BuNH2
2) 2 eq. MeLi, 2 eq t-BuLi
excess CO2
3) cat. HCl, MeOH reflux
HO
O
OH
P(OEt)2
MeO
OMOM
MeO
MeO
2) DBU
65%
O
H
N
O
78%
OMe
MeO
O
OMe
MeO
MeO
O
O
1) NaBH4
O
O
2) HCO2H H
77%
PPh3
DEAD
99%
O
O
N
O
HO
OH 2) n-BuLi
OMe
60%
CrO3, H2SO4
-30ºC
61%
name reaction MeO
1) KH
n-Bu3SnCH2I MeO
O
1) n-BuLi, THF
85-95%
70-75%
Will Gutekunst
N
H
O
O
O
NMe
MeO
H
(±)-O-methylpallidinine
Enantiospecific Total Synthesis and Absolute Configurational Assignment of (-)-Punctatin A
Leo A. Paquette, Takashi Sugimura. 3841-3842.
O
O
O
MeO
1) LiAlH(O-t-Bu3)
2) SEM-Cl, Hunigs Base
O
3)CH3SOCH2-Na+,
mycophenolic acid
17-19% overall
O
O
2) KH
ICH2SnBu3
DMSO
I
48%
1) LiAlH4
SEMO
SnBu3
SEMO
The Total Synthesis of Octosyl Acid A: A New Departure in Organostannylene Chemistry
Samuel Danishefsky, Randall Hungate; 2486-2487.
O
TMSO
OMe
H
85%
OMe
O
O
O
O
MeO2C
15 steps
OMe
MsO BnO
H
8.6%
O
H
MeO2C
NH
O
O
Bu2SnO
MeOH
OBn
OMsO
MeO2C
O
N
O
Sn
Bu
Bu
O
CsF
DMF
77%
O
2) MOM-Cl
Hunigs Base
SEMO
34%
OH
O
MeO2C
NH
N
1) BH3-THF, diglyme;
H2O2, NaOH, H2O
1) n-BuLi
2) PCC, DCM
3) NaOMe, MeOH
MOMO
O
SEMO
O
HO
MeO2C
MOMO
O
O
O
MeO2C
O
HO2C
NH
OBn
H O
O
1) hv, 253.7 nm
2) TBAF
N
O
OH
3) PCC, DCM
O
1) Pd(OH)2
2) LiOH, H2O
OH
NH
MOMO
OH
H
HO2C
N
O
O
O
OH
Octosyl Acid
1) NaBH4, CeCl3
2) DEAD, PPh3, PhCOOH
3) HClO4, THF/H2O
4) KOH, EtOH
62%
1) Me3SiCH2COOMe
cat. TBAF, THF
mechanism?
2) Pd(OAc)2, MeCN
32% for 5 steps
HO
OH
HO
(-)-punctatin A
MOMO
OTMS
O
JACS: 1986 Year in Review
Baran Group Meeting
Stereocontolled Asymmetric Total Synthesis of Protomycinolide IV
Keisuke Suzuki et. al. 5221-5229.
A Total Synthesis of Plumericin, Allamcim, and Allamandin
Barry M. Trost, James M. Balkovec, and Michael K.-T. Mao. 4974-4983.
S
1)
Ph
Ph
BF4
PhSeBr
KOH, DMSO
2) LDA, pentane
82%
O
DCM, py
-45ºC
88%
OH
1) NaH, BOMCl
2) EtMgBr, TMSCl
mCPBA, -78oC
warm to 0oC
PhSe
O
OH
O
O
O
-78o C
95%
O
1) mCPBA, DCM
then, CaCO3 reflux
EtMgBr, 0o C
O
then, CH3CHO
O
SPh
PhS
100%
O
HO
OH
BOMO
2) Ac2O, DMAP, py
n-BuLi/ Trapp solvent
4:1:1 THF:Et2O:hex
-100o C, then H2SO4
92%
TMS
BOMO
OH
O
steps
75%
SPh
Br
DCM, -78oC to -20oC
mechanism?
TMS
NMe2
OEE
1) MsCl, TEA
2) DiBAL, then AlEt3
O
65-70%
O
TMS
3) DiBAL, Br2
then add
OBOM
PhSSO2Ph
LDA, THF
Will Gutekunst
O
Protomycinolide IV
OH
OsO4, NMO, H2O;
O
NaIO4, H2O
then NaOAc
3:1 E:Z
80%
O
AcO
O
O
O
O
FVT, 500o C
.005 mmHg
O
O
Convergent, Enantiospecific Total Synthesis of the Hypocholesterolemic Agent (+)-Compactin
Paul A. Greico, Randall Lis, Robert E. Zelle, John Finn. 5908-5919.
81-90%
allamcin
OMe
O
O
OMe
OMe
O
MeO
0.01N HClO4
O
O
O
O
O
95oC - 100oC
77%
allamandin
MeO
MeO
OMe
Lewis acids
+
83%
O
OMe
MeO
O
NR
OMe
5 kbar (71000 psi)
neat
HO
O
O
O
O
jatropholone A
SPh
OMe
H
CO2Me
Toluene
125oC
7:3 regioisomers
86%
MeO2C
O
PhS
P(Ph)3
BuLi (9:1 E:Z)
3) CrO3, py, celite
PhO2S
1)
O
TMS
O
NR
O
72 hrs
80%, single diastereomer
OMe
1) Na(Hg), MeOH
2) LiAlH4
CO2Me
MeO
O
O
PhO2S
83%
O
heat, 110-220 oC
3) NaH, DMSO, 80oC
OH
71%
Total Synthesis of (+)-Jatropholones A and B, Exploitation of the High-Pressure Technique
Amos B. Smith et. al. 2040-3048.
OMe
1) TsCl, py
2) NaI, MEK reflux
O
O
55%
plumericin
O
3) Na, NH3(l)
OTr
O
O
OMe
1) LiAlH4, Et2O
2) NaH, MeI
OH
1) CCl3COCl
2,6 di-t-Bu-py
2) Mg(OCH3)2
O
O
O
2) TBAF
3) PhSH, AIBN
HMPA, 150oC
(3:2 E:Z)
42%
O
1) mCPBA, P(OMe)3, MeOH
2) DEAD, BzOH, PPh3
3) NaOMe, MeOH
4) Ac2O, DMAP, TEA
63%
JACS: 1986 Year in Review
Baran Group Meeting
MeO
OMe
H
MeO
1) MeLi, CuI, Et2O
MeO2C
OAc
MeO
OMe
H
O
O
KH, Toluene
HO
2) LiAlH4, Et2O
84%
H
O
OMe
H
O
OH
120oC
Me
Me
N
O
N
OH
OH
O
MeO
Na2SO3, K2HPO4
Me
N
H
O
O
N
O
O
O
Me
N
O
N
H
MeO
H
HO
N
SnCl4, DCM
9:1 d.r
56%
Cl
1) LiBEt3H, THF
2) DDQ, MeCN/H2O
MeO
OMe
O
Me
HO
Me
OMe
Me
N
H
Me
N
O
N
3) Ac2O, DMAP, py
4) Zn dust, TBSCl
Hunig's base, DMAP
79%
H
O
N
Me
OTBS
TBSO
Me
OMe
TBSO
O
cyanocycline
1) s-BuLi, MeI
2) s-BuLi, Ph2Se2;
O
N
H
H2O2, py
62%
O
N
H
O
6 steps
O
HO
N
H
O
O
(–)-grandiosol
Synthesis of
Using Titanium Reagents
John R. Stille, Robert H. Grubbs; 855-856.
1)Tebbe Reagent,
DMAP, then 90ºC
TsO
CO2t-Bu
1) CpMgCl, THF
mechansim?
1) OsO4, NMO
2) Et4NIO4
AcO
N
(±)-Δ(9,12)-Capnellene
OMe
Me
N
OH
p-TsOH, toluene
azeotrope water
81%
93% (12:1)
HO
NMe
O
34%
H2N
DCM sat. with
ethylene
acetophenone
-78ºC
OMe
O
N
Me
3) HF-py, MeCN, 50oC
then, aq Na2CO3 to
pH 10, O2
O
HO
N
H
CN
MeO
Efficient Asymmetric (2+2) Photocycloaddition Leading to Chiral Cyclobutanes. Application to
the Total Synthesis of (–)-Grandiosol
A.I. Meyers, Steven A. Fleming; 306-307.
O
MeO
O
O
O
N
MeO
96%
H
3) TFA, t-BuOOH
81%
OMe
O
2) SOCl2
Me
N
H
Me
N
H
2) H2, Pd/C, CH2O
80%
1) MsCl, TEA
2) (PhSe)2, NaBH4
OMe
O
1)
1) H2O2, aq. Na2CO3
Cbz
N
O
CN
OH
82%
NH2
7 steps
O
H
t-BuOK
OH
O
NMe
Stereoselective Synthesis of (±)-Cyanocycline
David A. Evans, Carl R Illig, John C. Saddler
NH
2) KHMDS, THF
68%
N
1) Li, NH3-THF
2) NaCN, pH 8.0 Tris
N
TBSO
compactin
Et2O, -24 to -16oC;
TBSO
O
OTBS
O
OH
Me
N
Me
74-77%
2 steps
1) LiBEt3H, THF
NMe
O
23%
ClO2S
N
OMe
O
2) 10% HCl, THF,
then Ag(CO3)2/celite
3) BBr3, DCM
MeO
Neat TFA
Me
O
H
1) (S)-2-methylbutyric anhydride
DMAP, TEA
OAc
O
OTBS
OTBS
TBSO
HO
OTBS
N
AcO
40% (50 brsm)
O
H
Will Gutekunst
2)Benzene, 75ºC
81%
t-BuO2C
H H O
NH2
16-24 hrs
H
O
9 steps
2) HOCH2CH2OH, TsOH
benzene, reflux
81%
H H
H
(±)-Δ(9,12)-capnellene
Cp2Ti
Cl
AlMe2
Tebbe
Reagent
JACS: 1986 Triquinane Year in Review
Baran Group Meeting
General Transannulation Approach to Angular Triquinanes. Total Syntheses of (±)-Pentalenene
and (±)-epi-Pentalenene.
Goverdhan Mehta, Kasibhatla Srinivas Rao; 8015-8021.
Intramolecular Photocycloadditions-Cyclobutane Fragmentation: Total Synthesis of (±)
Pentalenene, (±)-Pentalenic Acid, and (±)-Deoxypentalenic Acid
Michael T. Crimmins and Joe A. DeLoach;
O
HCOOH, BF3
6 steps
O
CO2Et
90oC, 2 h
55%
H
H
4 steps
O
O
hv
CO2i-Pr
H
O
Will Gutekunst
uranium filter
hexane
73%
Li, NH3,
THF, -78ºC
90%
HO
CO2i-Pr
CO2Et
H
CO2i-Pr
CO2Et
10 steps
CO2H
pentalene
Asymmetric Total Synthesis of (+)-Penalenene via Chiral Sulfinylallyl Anions. Hydrolytic Ring
Closure of Enol Thioether Ketones
Duy H. Hua; 3835-3837.
2 eq O
O
S
O
(−)
2 eq
O
H
H
O
O
H
O
H
OH
(–)-coriolin
pentalene
A General Approach to Linearly Fused Triquinane Natural Products. Total Syntheses of (±)Hirsutene, (±)-Coriolin, and (±)-Capnellene
Goverdhan Mehta, A. Narayana Murthy, D. Sivakumar Reddy, A. Veera Reddy; 3443-3452.
O
Tandem Radical Cyclization Approach to Angular Triquinanes. A short synthesis of
(±) Silphiperfol-6-ene and (±)-9-Episilphiperfol-6-ene
Dennis P. Curran, Shen-Chun Kuo; 1106-1107.
O
OEt
O
9
Br
reflux
2h, 90%
O
O
O
30 min
85%
500ºC, 0.1 torr
sublimation through
O
O
NH2NH2
H
H
66%
1:3 C9 epimers
45%
hv
EtOAc
benzene
O
Bu3SnH
3 steps
H
O
HO
H
LDA
45%
(±)
(−)
kinetic resolution via chiral sulfoxide
H
hv (300 nm), 6h
55-58%
H
4 steps
H
O
>20% acetone soln
(–) O
82% ee
S
H
O
2 eq NaH, 2 eq MeI
45 min, then
NaH, 18-crown-6
MeI, 195 h
O
O
HO
Ar
2) 88% HCO2H, CF3CO2H
60ºC, 24 h
57%
O
H
O
1) Zn, AcOH
H
2 eq LDA, -78o C
91%
Total Synthesis of (-)-Coriolin
Martin Demuth, Peter Ritterskamp, Eva Weigt, Kurt Schaffner; 4149-4145
O
O
S
pentalenic acid
silphiperfol-6-ene
O
H
O
317ºC, 12 min
37%
H
H
H
H
benzylbenzoate
quartz column filled
with quartz chips
quantitative
6 steps
O
H
H
O
hirsutene
JACS: 1986 Year in Review
Baran Group Meeting
Use of Chiral Single Chrystals To Convert Achiral Reactants to Chiral Products in High Optical
Yield: Application to Di-π-Methane and Norrish Type II Photorearrangements
Stephen V. Evans, Miguel Garcia-Garibay, Nalamasu Omkaram, John R. Sheffer, James Trotter, Fred
Wireko; 5648-5650.
Et3SiH
CH2O2i-Pr
i-PrO2C
+
O3
70%, 80% ee
Titanacyclobutanes Derived from Strained Cyclic Olefins: The Living Polymerization of Norbornene
Laura R. Gilliom, Robert H. Grubbs; 733-742.
xs
n
O
O
91%
O
RO
RO
N
N
N
N
OR
1) H2S, CH2CN
N N
OR 2) Pb(OAc) , CaCO
4
3
1) 37% HCl, DCM
O
O
O
-100ºC
Cl
O
ZnCl2
O
20ºC
86%, 200:1 dr
TiCl3, Zn/Cu
23%
after recrystallizion
of the sublimate
N3
O
B
B
H2O/DCM
quant.
O
Cl
LiCHCl2, -100ºC
O
then, ZnCl2, 25ºC
O
S
1) H2O2 pH 7.6
B O
BuMgCl, -78ºC
OR
OR
RO
RO
2) toluene reflux
then, (EtO)3P
name reaction
LiCHCl2
O
B
O
N3
O
O
HN P(OEt)2
N
O
O
18 h, 45%
Cl
Synthesis and Chemistry of Tetracyclo[8.2.2.22,5.26,9]-1,5,9-octadiene
John E. McMurry, Gerogy J. Haley, James R. Matz, Jon C. Clardy, Gregory Van Duyne, Rolf Gleiter,
Wolfgang Schafer, David H. White; 2932-2938.
OH
B
O
Cp2Ti
H2NNHPO(OEt)2
DMDO
OH
B
NaN3, Bu4NCl
O
1O
2
Cl
65ºC
DMAP
Et3SiOH
99% Chirally Selective Syntheses via Pinanediol Boronic Esters: Insect Pheromones, Diols, and
an Amino Alcohol.
Donald S. Matteson, Kizhakethil Mathew Sadhu, Mark L. Peterson; 810-819.
O
Cl
t1/2 ca 150 s
18 h, quant
HO
AlMe2
45 s
DMDO
Ar
Ar
Cp2Ti
ca -60ºC
Et3SiOOOH
Chemistry of Dioxiranes 4. Oxygen Atom Insertion into Carbon Hydrogen Bonds by
Dimethyldioxirane
Robert W. Murray, Ramasubbu Jeyaraman, Lily Mohan; 2470-2472.
80%, single enantiomer
O
Generation of 1Δg O2 from Triethylsilane and Ozone
E. J. Corey, Mukund M. Mehrotra, Ahsan U. Khan; 2472-2473.
-78ºC
CO2i-Pr
CO2i-Pr
Will Gutekunst
OH
2) LiAlH4
4 eq ZnCl2
59% for 3 steps
N3
NH2
S
N N
Chiral Synthesis bia Organoboranes. 8. Synthetic Utility of Boronic Esters of Essentially 100%
Purity. Synthesis of Primary Amines of Very High Enantiomeric Puritys
Herbert C. Brown, Kee-Won Kim, Thomas E. Cole, Bakthan Singaram; 6761-6764.
H
B
5 steps
O
B
1) H2NOSO3H
NH2
2)H2O, NaOH
99% ee
JACS: 1986 Year in Review
Baran Group Meeting
Epoxy Silyl Ether Rearrangements: A New, Stereoselective Approach to the Synthesis of
β-Hydroxy Carbonyl Compounds
Keiji Maruoka, Masaichi Hasegawa, Hisashi Yamamoto; 3827-3829.
Tandem Reactions of Alkynyliodonium Salts. Extremely Efficient Cyclopentene Annulations
Masahito Ochiai, Munetaka Kunishima, Yoshimitsu Nagao, Kaoru Fuji, Motoo Shiro, Eiichi Fujita
The Yamamoto Rearrangement
R1
O R3
R2
O
Ti
TiCl4, DCM
OTMS
R1
-78ºC, 10-30 min
50-95% yield
R4 R5
OH
O R3
R1
R2
OTMS
R2
R4 R5
OH
O
O
R5
R3 R4
HN
HO
79%
R3
DME, 160ºC, 24 h
R1
R3
N
+
+ MeCN
Me
C4H9
N
Catalytic Asymmetric Aldol Reaction: Reaction of Aldehydes with Isocyanoacetate Catalyzed by
a Chiral Ferrocenylphosphine-Gold(I) Complex
Yoshihiko Ito, Masaya Sawamura, Tamio Hayashi; 6405-6406.
93%
O
+ MeCN
Me
CN
97%
N
N
H
98%, Mn = 1600
mp = 175
n
Oxazoline Route to Azomethine Ylides
Edwin Vedejs, Janet Wisniewski Grissom. 6433-6434.
R
X
N
R2
O
R3
R
R
PhSiH3, CsF
N
R2
O
R3
R1
R1
[2+2]
Epoxidation of Olefins with Cationic (salen)MnIII Complexes. The Modulation of Catalytic
Activity by Substituents
K. Srinivasan, P. Michaud, J.K. Kochi; 2309-2320.
Simple and Selective Method for RCHO -> (E)-RCH=CHX Conversion by Means of a CHX3-CrCl2
System
Kazuhiko Takai, Kenji Nitta, Kiitiro Ultimoto; 7408-7410.
O
H2N
(most examples 45-75%)
NH3
R2
H
H
N
O
Palladium-Catalyzed Coupling of Vinyl Triflates with Organostannanes. Synthetic and
Mechanistic Studies
William J. Scott, J. K. Stille; 3033-3040.
O
C4H9 NH2
mechanism?
Seminal and/or Important Publications
O
3 mol % RuH2(PPH3)4
+ 2 eq H2O
IC6H5
BF4
93%
O
O
OTMS
R2
t-BuOH
O
Ph
Ruthenium Catalyzed Amidation of Nitriles with Amines. A Novel, Facile Route to Amides and
Polyamides
Shun-Ichi Murahashi, Takeshi Naota and Eiichiro Saito. 7846-7847.
+
O
O
O
81%
Me Ph
R1 CN
t-BuOK
O
O
OTMS
O
Will Gutekunst
R1
N
R2
O
R3
[3+2]
Nonlinear Effects in Asymmetric Synthesis. Examples in Asymmetric Oxidations and
Aldolization Reactions
C. Puchot, O. Samuel, E. Dunach, S. Zhao, H. B. Kagan; 2353-2357.
Catalytic Asymmetric Induction. Highly Enantioselective Addition of Dialkylzincs to Aldehydes
M. Kitamura, S. Suga, K. Kawai, R. Noyori; 6071-6072.