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Dane HolteBaran Group Meeting JACS: 1987 A Year in Review
Overview: 1987, vol. 109– 8123 pages– ~60 total synthesis papers
Publication record:Barry Trost E.J. Corey Leo Paquette Samuel Danishefsky Phil MagnusClayton Heathcock K.C. Nicolaou Larry Overman Stuart SchreiberK. Barry Sharpless Gilbert Stork
Key methodologies developed and/or refined:
Stereospecific Cross-Coupling of Vinyl Halides with Vinyl Tin ReagentsCatalyzed by Palladium. J.K. Stille and B.L. Groh, 813–817.
Palladium-Catalyzed Coupling of Aryl Triflates with Organostannanes.A.M. Echavarren and J.K. Stille, 5478–5486.
Highly Enantioselective Borane Reduction of Ketones Catalyzed by Chiral Oxazaborolidines. Mechanism and Synthetic Applications. E.J.Corey, R.K. Bakshi, and S. Shibata, 5551–5553.
Asymmetric Hydrogenation of β-Keto Carboxylic Esters. A Practical,Purely Chemical Access to β-Hydroxy Esters in High Enantiomeric Purity. R. Noyori, T. Ohkuma, M. Kitamura, H. Takaya, N. Sayo, H. Kumobayashi, and S. Akutagawa, 5856–5858.
A Stable and Easily Prepared Catalyst for the Enantioselective Reduction of Ketones. Applications to Multistep Syntheses. E.J. Corey,R.K. Bakshi, S. Shibata, C-P. Chen, and V.K. Singh, 7925–7926.
1310876554444
OO
O
O
HNHO
MeO
HNEt
MeOO
Me
OH
S
MeI
OOMe
OMe
O
OHMeOHO
Me
O
O
NH
O
OMeHO
MeSSS
H
Calichemicins, a Novel Family of Antitumor Antibotics.1. Chemistry and Partial Structure of Calichemicin γ1
I.2. Chemistry and Structure of Calichemicin γ1
I.M.D. Lee, T.S. Dunne, M.M. Siegel, C.C. Chang, G.O. Morton,and D.B. Borders, 3464–3466 and 3466–3468.
Notable Isolation Papers:
HO
MeO
O
Me
OH
O
MeON
Me
O O
OMe
OMe
H
OMe
Me
Structure of FK506: A Novel Immunosuppressant Isolated from Streptomyces. H. Tanaka, A. Kuroda, H. Marusawa, H. Hatanaka, T. Kino, T. Goto, and M. Hashimoto, 5031–5033.
iPr NMe
Me
NHO
N
OiPr
MesBu
OMe N
O
OMeMe
HN O
S
N
The Isolation and Structure of a Remarkable Marine Animal Antineoplastic Constituent: Dolastatin 10. G.R. Pettit, Y. Kamano, C.L. Herald, A.A. Tuinman, F.E. Boettner, H. Kizu, J.M. Schmidt, L. Baczynskyj, K.B. Tomer, R.J. Bonttems,6883–6885.
structurally related to:Esperamicins, a Novel Class of Potent Antitumor Antibiotics.2. Structure of Esperamicin X.3. Structures of Esperamicins A1, A2, and A1a.J. Golik, J. Clardy, G. Dubay, G, Groenwold, H. Kawaguchi, M. Konishi, B. Krishnan, H. Ohkuma, K. Saitoh, and T.W. Doyle, 3461–3462 and 3462–3464.
Dane HolteBaran Group Meeting JACS: 1987 A Year in Review
Total Synthesis and Absolute Configuration of 7,20-Diisocyanoadociane.E.J. Corey and P.A. Magriotis, 287–289.
OH
Me
MeMe
+O OO
Me O
iPrO O
1. PhSeSiMe3 (1.3 eq), HO(CH2)2OH (xs), I2 (cat.)2. mCPBA3. Me2S, (iPr)2NH
Me O
iPrO OO
Me (CH2)2OTBMSH
PhMe, 150 ºC20 h (90%)
TBMSO(H2C)2 Me
OO
H
O
O
[4+2]
Me
OO
H
BzO
OOOBz
Me
PhMe, 185 ºC36 h (54% + 36% other diaster.)
MeH
MeCN
MeH
NCMe
7,20-Diisocyanoadociane
[4+2]
Syntheses that will be discussed today:
MeH
MeCN
MeH
NCMe
7,20-Diisocyanoadociane
O
O
Me
MeHO
Me
O OH OH
OH
OH OH
OH
CO2H
OAmphotericin B
OH
O
OH NH2
OHMe
HOMe OH
Me
HOOH
Aphidicolin
N
N
MeOMe
HOHCO2Me
OCOMeEt
H
(–)-Vindoline
NN
N
O H
H H H
O
O
MeO
Me Me
CNHO
(±)-Cyanocycline A
NH
AcN
CO2Me
(±)-Clavicipitic Acids
MeOH
H
H
Me
HMe Me(±)-2-Desoxystemodinone
O
OO
MeO
MeOOMe
O
O
(–)-Steganone
Me MeMe
MeMe
H
(±)-Laurenene
Pagodane
N NH
R
MeO
OOMeOCONH2
Mitomycins
Dane HolteBaran Group Meeting JACS: 1987 A Year in Review
O
O
Me
MeHO
Me
O OH OH
OH
OH OH
OH
CO2H
O
Stereocontrolled Construction of Key Building Blocks for the Total Synthesis of Amphoteronolide B and Amphotericin B. K.C. Nicolaou, R.A. Daines, J. Uenishi, W.S. Li, D.P. Papahatjis, and T.K. Chakraborty, 2205–2208.
Total Synthesis of Amphoteronolide B. K.C. Nicolaou, R.A. Daines, and T.K. Chakraborty, 2208–2210.
Total Synthesis of Amphotericin B. K.C. Nicolaou, R.A. Daines, T.K. Chakraborty, and Y. Ogawa, 2821–2822.
OH
O
OH NH2
OHMe
β-gylcosideformation
macrolactonization
Horner-Wadsworth-Emmons (HWE)
OHO
Me
MeRO
Me
O O O
OR
O O
OR
CO2Me
O
MeO
O (MeO)2PO
HO
HWE HWEacid-induced
THP formation
HWEHWE
OHMe
MeRO
Me
CO2Et
RO
O O
O
O O
O
ORO
BnO
O
(EtO)2PO
O
(MeO)2PO
PhO
OR
OH H
OBnBnO
(+)-diethyltartrate
EtOOEt
O
OH
OH
O
O
HO OH
OHHO
O
HO OH
OHHO
(+)-xylose
(–)-xylose
OBnOH OH OH
OBnOH OH OH
OBnHO
Dane HolteBaran Group Meeting JACS: 1987 A Year in Review
Stereocontrolled Total Synthesis of (±)-Cyanocycline A. T. Fukuyama,L. Li, A.A. Laird, R.K. Frank, 1587–1589.
NOH
tBuO2C
Me
CO2tBu LDA, THF, -78 ºC;then ZnCl2 (1.5 M);
OMeMe
MeOOBz
H
O
then:OMe
Me
MeOOBz
OH
NCO2tBu
OH
tBuO2C OMeMe
MeOOBz
O
NCO2PG
CO2Me
OH2N H
H
CSA, quinoline,PhH, reflux, (85%)
(77%)
(34% over 10 steps)
MeOMe
MeOOBz
HN
N
H
H
O
then NaBH3CN (64%)mechanism?
MeOMe
MeOOBz
HN
N
H
H
O
NHO
MeOMe
MeOOH
HN
N
H
H
O
NH CO2PG 1. H2, Ra-Ni, Et3N
2. PhCH2OCH2CHO, AcOH, MeOH(66% over 2 steps)
CH2OBz
CO2Me
NOCl, -35 ºC;CO2PG CO2PG
CO2MeCO2Me
(37% over6 steps)
Me
MeOOAc
HN
O
NNCO2PG
AcO
MeOH H H
CN
1. Lawesson's reagent mechanism?
PS
PS Ar
SAr
S
Me
MeOOAc
N
NNCO2PG
AcO
MeOH H H
CN
2. "Careful" Ra-Ni (74% over 2 steps)
Me
MeOOAc
N
NNCO2PG
AcO
MeOH H H
CN
O , MeOH, 60ºC
O
(99%)
NN
N
O H
H H H
O
O
MeO
Me Me
CNHO
(±)-Cyanocycline A
(42% over 4 steps)
Dane HolteBaran Group Meeting JACS: 1987 A Year in Review
Enatioselective Total Synthesis of Aphidicolin. R.A. Holton, R.M. Kennedy, H-B. Kim, M.E. Kraft, 1597–1600.
TBSOMe
O
Me
1. LDA, PhMe, -78 ºC2.
-78 ºC to r.t.O
STolO
O
3. vinyllithium (7 eq), 1 hr4. HF/MeOH, 20 min5. NaOMe, 0 ºC, 1.5 hr(45% after chromatography)
O
S(O)TolO
OMe
Me
TBSOMe
OMe
Me
O
Me
O
S(O)TolO
Me
Me
O
Me
O
S(O)Tol
HOMe OH
Me
HOOH
with vigorNH
NMeO
Et
OFirst 5 steps can be done in one-pot, before lunch: MeO2C
Me
HO
tBuOCl; then DBU (3 eq),0 ºC, 20 min
(75% with one recycle)
N
N
MeOMe
H OHCO2Me
OCOMeEt
H
(–)-VindolineN
N
MeO
OEt
H
CO2Me
mechanism?
Synthesis of (–)-Vindoline. P.L. Feldman and H. Rapoport, 1603–1604.
Total Synthesis of (±)-2-Desoxystemodinone. A Novel Hydroxyl-Assisted, Intramolecular Ene Reaction. J.D. White and T.C Somers, 4424–4426.
CHOOH
Me
Me
HMe Me
PhMe, 110 ºC16 h (94%)
MeOH
H
H
Me
HMe Me
H
OH
Me
HMe Me
OH
OH
"The pivotal role of the hydroxyl substituent in this process was verfied by its reductive removal..."
(Title withheld for your own good). P.J. Wagner and K. Nahm, 4404–4405.(Title withheld for your own good). P.J. Wagner and K. Nahm, 6528–6530.
O
O
OH
Ohv
mechanism?
Dane HolteBaran Group Meeting JACS: 1987 A Year in Review
Palladium-Catalyzed Reactions in the Synthesis of 3- and 4-substituted Indoles. 2. Total Synthesis of N-Acetal Methyl Ester of (±)-Clavicipitic Acids. P.J. Harrington, L.S. Hegedus, and K.F. McDaniel, 4335–4336.
NH
AcN
CO2Me
(±)-Clavicipitic Acid N-Acetal Methyl Ester
BrMe
NO2
1. Br2, hv, CCl42. PPh3
3. CH2O(g), Et3N (80% overall)
Br
NO2
1. Fe, AcOH2. TsCl, py.
Br
NHTs
5% PdCl2(MeCN)2benzoquinone
(80% over 3 steps)
Br
NTs
1. Hg(OAc)2, HClO4 (cat.)
2. I2 (97%)
Br
NTs
ICO2Me
NHAc
5% Pd(OAc)2, NEt3(60%)
Br
NTs
CO2Me
NHAc
OH
MeMe
8% Pd(OAc)2, NEt3P(o-tol)3 (83%)
NTs
CO2Me
NHAcOHMe
Me
15% PdCl2(MeCN)2
(95%)NTs
AcN
CO2Me
NaBH4, hv
Na2CO3, -20 ºC(74%)
Total Synthesis of (±)-Mitomycins via Isomitomycin A. T. Fukuyama and L. Yang, 7881–7882.
OMeMe
MeOOBz
N3
O
Ph
OEtS OTMS
SnCl4, -78 ºC2. 3N HCl, r.t. (98% overall) OMe
Me
MeOOBz
N3
O
Ph
OO
SEt1.
PhMe, 110 ºC2 hr (93%)mechanism?
OMeMe
MeOOBz
N
O
Ph
OO
SEt
N NH
R
MeO
O
OMe
OCONH2
R = OMe Mitomycin A
N
HN
O
O OMeO
O NH2
Me
MeO Al(OiPr)3, MeOH,r.t. 2 d (91%)
mechanism?
OMeMe
MeOOBz
N
O
Ph
NO
OH
OAr
H2N O Ar
40 ºC, 1 hr (87%)
Dane HolteBaran Group Meeting JACS: 1987 A Year in Review
Cl
ClCl
ClClCl
SCl
Cl Cl
Cl
[4+2]Cl
ClCl
ClClCl
Cl
Cl
Cl
Cl
OOS
O O
PhMe, 110 ºC-SO2
Cl
ClCl
ClClCl
Cl
Cl
Cl
ClHH
Cl
ClCl
ClClCl
ClCl
Cl
Cl
85% overallkg scale?!
Li, tBuOH
SCl
Cl Cl
ClOO1.
2. Li, tBuOHH
HPd/C (10 eq)
"an intimate mixture"(ie. neat), 250 ºC,
sealed tube
254 nm hv
[6+6]
[4+2]
O
O
O
OO
O
[4+2]
Cu2O, quinoline,H2O, bipy.
150 ºC
1. B2H6, THF2. NaOH, H2O2
3. CrO3, H2SO4O
O
H OMe
O
NaH
O
OHOOH AcOH; then
TsN3, NEt3
O
ON2
N2
hv, MeOH
Wolff rearr.MeO2C CO2Me
1. KOH, EtOH
2. Pb(OAc)4, CCl4, I2, hvI I
Na-K, tBuOH
See also, Platonic Hydrocarbons group meeting (Shenvi, 2006)
"Pagodane": The Efficient Synthesis of a Novel, Versatile Molecular Framework. W. Fessner, G. Sedelmeier, P.R. Spurr, G. Rihs, and H. Prinzbach, 4626–4642.
Dytropic hydrogen transfer
Pagodane(24% overall)
OO O
Dane HolteBaran Group Meeting JACS: 1987 A Year in Review
MeMe
Me
MeMe
H
(±)-LaureneneCrimmins, 6199–6200
Intramolecular Photocycloaddition. Cyclobutane Fragmentation: Total Synthesis of (±)-Laurenene. M.T. Crimmins, and L.D. Gould, 6199–6200.
MeMe
Me
O
Me
MeO2C
O
MeMe
13 steps
(27%)
MeMe
Me
O
Me CO2MeU filter,
>350 nm hv
100 ºC(87%)
1. LiAlH4, Et2O2. Swern Ox.3. Ph3P=CHCO2Et (89% overall)
MeMe
Me
O
Me CO2Et
1. Na, NH3, -33 ºC
2. H2, Pd/C, EtOH (80% overall)
MeMe
Me
O
Me CO2Et
1. LiAlH4, Et2O2. Swern Ox.3. TsOH, PhH (75% overall)
MeMe
MeMe
H H
O
various alkylations
MeMe
MeMe
H Me
RR
NaBH4,CeCl3
Luche(23%)
MeMe
MeMe
H H
H OH
MeMe
Me Me
H
HO1. KH,Bu3SnCH2I
2. nBuLi (57%) mech?
1. TsCl, py.
2. LiEt3BH (72% overall)
An Asymmetric Synthesis of (–)-Steganone. Further Application of Chiral Biaryl Synthesis. A. I. Meyers, J.R. Flisak, and R.A. Aitken, 5445–5452.
O
OO
MeO
MeOOMe
O
O
(–)-Steganone
OO
MgBr
OO
OMeMeO
MeOOMe
N
OPh
OMe
OO
MeO
MeOOMe
N
O
OO
THF, reflux
(65%)(7:1 mix. of diast.)
After asymmetric biaryl coupling,there are 9 steps before closing the 8-membered ring, with <10%racimization.
Ph
MeO
Synthesis of in-[34,10][7]Metacyclophane: Projection of an Aliphatic Hydrogen toward the Center of an Aromatic Ring. R.A. Pascal, R.B. Grossman, and D. Van Engen, 6878–6880.
H
HH
Dane HolteBaran Group Meeting JACS: 1987 A Year in Review
Comprehensive list of all total syntheses (*formal):
O
NO
Cl
H NH3
CO2H
AcivicinWhitney, 276–277
MeH
MeCN
MeH
NCMe
7,20-DiisocyanoadocianeCorey, 287–289
(±)-CatharanthineRaucher, 442–446
O
OO
OMe
NH
OMe
Me
OH
Me
OH
MeAcO
MeMeO
O
MeOH
*Rifamycin SDanishefsky, 862–867
Roush, 953–955
NH
N
CO2Me EtN
O
H H
Me
HO
CO2
S
NH3
(+)-ThienamycinGeorg, 1129–1135
OO
O Ph
Me
O
H
H
(+)-PhyllanthosideSmith, 1269–1272Smith, 1272–1274
O
O
OHO
AcOHO
AcOHO
Me
O
Me
O
H
OH
OMe
MeOH
Me
MeOH
OH
OHMe
O
Et
HOMe
(+)-(9S)-DihydroerythronolideStork, 1565–1567
OMeO2C
Me
MeH H
Me
Me
OH
Me
OH
Me
OH
Me
OH
MeMeZincophorin
Danishefsky, 1572–1574
NN
N
O H
H H H
O
O
MeO
Me Me
CNHO
(±)-Cyanocycline AFukuyama, 1587–1589
HOMe OH
Me
HOOH
AphidicolinHolton, 1597–1600
N
N
MeOMe
H OHCO2Me
OCOMeEt
H
(–)-VindolineRapoport, 1603–1604
OH H
MeO2C
Me Et
Me
H Et
HO
HN
*IndanomycinDanishefsky, 2082–2089
O
O
Me
MeHO
Me
O OH OH
OH
OH OH
OH
CO2H
OAmphoteronolide B, Amphotericin BNicolaou, 2205–2208Nicolaou, 2208–2210NIcolaou, 2821–2822
HN N
HO2C
MeO OH
R
O
R = NH2 PDEIR = Me PDEII
Magnus, 2711–2717Boger, 2717–2727
OH
O
OH NH2
OHMe
CO2MeEt
O
Et
Me
Me
4-Methyl Juvenile HoromoneOgura, 2853–2854
OO
OO
O
OHtBu
OHO
H
(±)-BilobalideCorey, 7534–7536
Dane HolteBaran Group Meeting JACS: 1987 A Year in Review
Comprehensive list of all total syntheses (Cont'd):
NMeO
MeO
O(±)-3-Demethoxyerythratidinone
Danishefsky, 917–918
O NH
O
O
HO
HO OH*(+)-Showdomycin
MeMe
OH
HO Me
HO H
(–)-Punctatin A,(+)-Punctatin D
Paquette, 3017–3024
H
Me Me
OH Me
Me
AfricanolPaquette, 3025–3036
MeOH
HMe Me Me
DactylolPaquette, 3025–3036
O
O
Me H
H
OH
O(±)-Grosshemin
Rigby, 3147–3149
O
�O
OH
OH
O
OO
MeOHHO
OMeH H
H
(±)-GranaticinYoshii, 3402–3408
O
AcHN
MeHO
OMe
(—)-N-Acetal-O-methylacosamineTrost, 3792–3794
NH
AcN
CO2Me
(±)-Clavicipitic Acid derivativesHegedus, 4335–4338
MeOH
H
H
Me
HMe Me(±)-2-Desoxystemodinone
White, 4424–4426
O
OHOHMe
(±)-CafestolCorey, 4717–4718
HOHO
C5H11
HO2C
d-(+)-CarbacyclinFuchs, 4755–4756
NMe
H(±)-Porantherine
Stevens, 4940–4948
O
OHO
OHOH
HMe
NHO
NH2Me(+)-Actinobolin
Kozikowski, 5167–5175
O
OOEt
OEtO
OOH
HO(–)-Specionin
Curran, 5280–5282
O
OO
MeO
MeOOMe
O
O
(–)-SteganoneMeyers, 5446–5452
HN
HO2C
O NH
CO2H
CO2H
Acromelic Acid ATakano, 5523–5524
O
OMe
MeOH
MeOEt
MeHO
d,l-MethynolideVedejs, 5878–5880
NO
O
H
OH
StreptazolinOverman, 6097–6107Overman, 6017–6114Overman, 6115–6118
Me
NH
N
O
O
OMeMeO2C
H
HH
MeONH
N
OHMeO2C
H
HH
(±)- ReserpineMartin, 6124–6134
(±)-α-YohimbineMartin, 6124–6134
OMe
OMe
OMe
Dane HolteBaran Group Meeting JACS: 1987 A Year in Review
Comprehensive list of all total syntheses (Cont'd):
O
O
H HO
OC5H11
(+)-GloesproneSeebach, 6176–6177
OH
Me
CO2H
HO
(±)-AtractyligeninCorey, 6187–6189
MeMe
Me
MeMe
H
(±)-LaureneneCrimmins, 6199–6200
O
OO
MeMeMe
OH
OMe
OH
O
O
Me Me
OMe
OH
Br
AplysiatoxinKishi, 6205–6207
Me
Et H
H H
H
O
NH
NHO
O HH
*IkarugamycinWhitesell, 6403–6408
NH
Me
Pr
(+)-PulmiliotoxinSchultz, 6493–6502
HN N
MeO OH O
O
N
NH
N
O
HN
MeOMe
OH
O
NH2
CC-1065Kelly, 6837–6838
NNH
OH
OH
HN
OHO Me
OOHN O O
HN
OHMe
O
Me
HO
NH OHO
BuEchinocandin D
Evans, 7151–7157
O
O(–)-5-Hexadecanolide
Taber, 7488–7494
OO
Me
MeMe
HMe
ONH
N
O
HO2C NHMeCalicimycin
Boeckman, 7553–7555
�
OHO Me
OHOHOMe
H
OOHOH
HO
OlivinRoush, 7575–7577
N NH
R
MeO
O
OMe
OCONH2
R = OMe Mitomycin AR = NH2 Mitomycin CFukuyama, 7881–7882
NH
N
H
HEt
(–)-AspidospermidineFuji, 7901–7903
NH
N
H
Et
(+)-QuebrachamineFuji, 7901–7903
N
N
O Et
H
(–)-EburnamonineFuji, 7901–7903
O
OMe
OHOAc
OHMe MeH
MeOH
Me
*ForskolinZiegler, 8115–8116
OH
OMeMe
HOO O
OO
Me
MeH
MeMeH
O
O
Me
O
O
H
OMe
Me
HOMe
OMe
Avermectin A1aDanishefsky 8117–8119Danishefsky 8119–8120