Post on 11-May-2022
Philipp Gritsch
Review:Angew. Chem. Int. Ed. 2000
Kalesse & Gaich Seminar
Group seminar Kalesse & Gaich
2. 11. 2011
Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch
Publication Record
- 4617 pages
- 1086 papers in total
- 33 „Total Synthesis“ as research topic
Notable events
- Wladimir Putin is elected President of Russia
- First year of the FPÖ-ÖVP Government in Austria
- American Beauty wins Academy Award for Best Picture
- Maschen-Draht-Zaun by Stefan Raab is No. 1 for 14 weeks
- First permanent resident aboard the ISS
- EXPO 2000 in Hannover
2Kalesse & Gaich Seminar
Most cited papers
1) (2729) Ionic Liquids – new „Solution“ for Transition Metal Catalysis;
Wasserscheid, P.; Keim, W. Angew. Chem. Int. Ed. 2000, 39(21), 3772 – 3789;
2) (1488) Olefin Metathesis and Beyond;
Fürstner, A. Angew. Chem. Int. Ed. 2000, 39(17), 3012 – 3043;
3) (1363) Multicomponent Reactions with Isocyanides;
Domling, A.; Ugi, I. Angew. Chem. Int. Ed. 2000, 39(18), 3168 – 3210;
Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch
Detailed Syntheses Concise Syntheses
NH2N
OMe
HO
HH
Me
O O
O O
OO
n-Pr
H
HMeO2C
HOOAc
H
OH
O
OH
H
O
OH
O
Bryostatin 3
3Kalesse & Gaich Seminar
OP
O
OH
OH
Cl
FR901483
NH
O
N
NH
O
O
MeO
( )-Spirotyprostatin B
Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch
Asymmetric, Stereocontrolled Total Synthesis of Paraherquamide A; Williams, R. M.; Cao, J.;Tsujishima, H. Angew. Chem. Int. Ed. 2000, 39(14), 2540 - 2544
N
Boc
CO2Et
O
(a) Baker's Yeast
60-80%90% ee
N
Boc
CO2Et
OH
N
Boc
CO2Et
OH
I
OTBS
(b) LDA, THF, HMPA
OTBS
(c) 5.7 equiv MOMCl, (i-Pr)2NEt, CHCl2(d) 2.7 equiv ZnBr2, CH2Cl2(e) K2CO3, 2.0 equiv BrCH2COBr, CH2Cl2
N CO2Et
OBr
58%86%
(3 steps)
(f) NH3 in MeOH(g) 3.0 equiv NaH, PhMe N
ONH
O79 %
(2 steps)
(h) 1.3 equiv n-BuLi, THF, 1.1 equiv ClCO2Me, -78 °C;then 5 equiv LiHMDS, 4.0 equiv ClCO2Me, -78 °C N
OMOM OTBS
ONCO2Me
O
CO2Me
93%
4Kalesse & Gaich Seminar
OMOM OTBS OMOM OTBS(2 steps) OMOM OTBS
N
O
OOTBS
(i) 0.7 equiv n-Bu3P
NH
N
O
OMOMO
TBSO
CO2Me
H
NH
Me2N
O
O
OTBS
70%3:1
(j) 5.0 equiv LiCl, H2O, HMPA, 105 °C, 5 h
89%
N
O
OOTBS
NH
N
O
OMOMO
TBSO
H
H
syn 52%anti 78%
Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch
(k) 2.5 equiv Me3OBF4, CH2Cl2, Cs2CO3, 25 °C(l) 3.0 equiv Boc2O, DMAP, CH2Cl2, 0 °C(m) 3.3 equiv TBAF, THF, 25 °C
N
O
OOH
N
N
O
OMeMOMO
HO
H
Boc
N
O
OOTBS
N
N
O
OMeMOMO
Cl
H
Boc
(n) 1.1 equiv MsCl, collidine, CH2Cl2, 0 °C(o) 2.0 equiv TBSOTf, 2.6-lutidine, CH2Cl2, 0 °C
68-71%
(p) 20 equiv NaH, THF, reflux, 30 h
87%
N
O
N
OMOM
H
H
OMe
Boc
OTBS
(q) 3.1 equiv AgBF4, 4.68 equiv PdCl2, MeCN,then NaBH4, EtOH
O
5Kalesse & Gaich Seminar
exclusive synO
N
N
H
N O
O
N
N
OMOM
H
H
OMe
Boc
OTBS
(r) 0.1M HCl, THF(s) 2-hydroxypyridine, PhMe, 120 °C, 2 h63 % (3 steps)
(t) 5.0 equiv DIBAL-H, CH2Cl2, 0 °C50-70%
N O
O
N
N
OMOM
H
H
O
Boc
OTBS
H
O
O
(u) NaH, MeI, DMF, 0 °C, 96%(v) 6 equiv Bromocatechole borane,
CH2Cl2, 0 °C, 91%
(w) 5.0 equiv DMP, 85%(x)TFA, CH2Cl2, 97%
HN O
O
N
N
OH
O
OH
Me
(y) 1.5 equiv t-BuOCl, pyridinethen 5.0 equiv p-TsOH THF, H2O, refl.
(z) 5.0 equiv (PhO)3PMeI, DMPU(aa) MeMgBr, THF
Paraherquamide A
NH
O
O
O
N
N
OMe
OH
Me
H
Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch
A Concise Stereoselective Route to the Pentacyclic Framework in Arisugacin A and Territrem B;Hsung, R. P.; Zehnder, L. R.; Wang, J.; Golding, G. M. Angew. Chem. Int. Ed. 2000, 39(21), 3876 - 3879
O5 steps
overall 46%
O
O
(±)
(a) n-decane, refl., 23 h
61%
OO
(b) m-CBPA, CH2Cl2, 0°C, 24hpH buffer 7
59%
OO
O
3:1 to 6:1
(c) LiAlH4, Et2O,-78 °C to r t 2 h
OHOH
(d) Ac2O, Pyr, r.t., 24 h(e) DMP CH2Cl2 r t 2 h
OOAc
(f) K2CO3, MeOH,r t 24h
OHO (g) PCC, CH2Cl2r t 40 h
Nicolaou, K.C.; Li, W.S. J. Chem. Soc. Chem. Commun. 1985, 421
6Kalesse & Gaich Seminar
78 C to r.t., 2 h
O
(e) DMP, CH2Cl2, r.t., 2 h
90%
O
r.t., 24h
95%
r.t., 40 h
O
O
O
(h) Piperidinium AcetateNa2SO4, EtOAc, 80 °C, 1 h
O
O
NR2
O
R
OMe
OMe
OH
(i) EtOAc, 80 °C, 20 h
O
O
O
OO
O
OMe
OMe
R
68 - 71%
Arisugacin A R = HTerritrem B R = OMe
Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch
An Enantiospecific Synthesis of the Potent Immunosuppressant FR901483;Sorensen, E. J.; Scheffler, G.; Seike, H. Angew. Chem. Int. Ed. 2000, 39(24), 4593 - 4596
7Kalesse & Gaich Seminar
Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch
8Kalesse & Gaich Seminar
Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch
A New Enantioselective Approach to Total Synthesis of the Securinega Alkaloids: Application to (-)-Norsecurinine and Phyllantine;
Weinreb, S.M.; Han, G.; LaPorte, M. G.; Folmer, J. J.; Werner, K. M.; Angew. Chem. Int. Ed. 2000, 39(1), 237 - 240
9Kalesse & Gaich Seminar
Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch
10Kalesse & Gaich Seminar
Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch
HO OR
R = H
R = TBS(a) TBSCl, imidazole,
CH2Cl2, r.t., 1 h, 55%
(b) TBHP, Ti(Oi-Pr)4, D-(-)DET,MS 4 Å, CH2Cl2, -20 °C, 2 h, 83%
HO OTBSO
(c) Ti(Oi-Pr)4, PivOH,PhH, 0 °C, 2 h, 83%
HO OTBSOPiv
HO
OROPiv
O
O
(d) 2,2-dimethoxypropane,CSA, CH2Cl2, 0 °C, 2 h, 88%
R = TBS
R = H(e) BuN4F, THF, r.t.
3 h, 99%
(f) TBHP, Ti(Oi-Pr)4, L-(+)DET,MS 4 Å, CH2Cl2, -20 °C, 3 h, 89%
OHOPIv
O
O O
(h) A OH/H O 4 1 t 5 h
PhS
Li
Total Synthesis of (+)-Eurylene and (+)-14-Deacetyleurylene;Morimoto, Y.; Muragaki, K.; Iwai, T.; Morishita, Y.; Kinoshita, T. Angew. Chem. Int. Ed. 2000, 39(22), 4082 - 4084
11Kalesse & Gaich Seminar
(g) Ti(OMPM)4, MPMOH,PhH, 60 °C, 12 h
OHOPIv
O
O
MPMO
OH(h) AcOH/H2O 4:1, r.t., 5 h(i) MsCl, pyr, CH2Cl2, 0 °C to r.t., 5 h(j) K2CO3, MeOH, r.t., 1 h
OPIvMPMO
O O
(k) TMEDA, THF, - 78 °C, 30 minthen 0 °C, 2 h
41 % (4 steps)
OHMPMO
HO OH
PhS SPh(l) Na, THF/i-PrOH 2:1 refl, 15 h, 86%(m) Ac2O pyr, r.t., 12 h, 91 %(n) DDQ, MS 4 Å, CH2Cl2, 0 °C, 2 h, 68%
OAcHO
HO OH
(o) [(CF3CO2)ReO3.2CH3CN], TFAA, 'CH2Cl2/MeCN 9:1, -40 °C, 1.5 h, 84%
OAcHO
OHOHHO
(p) PCC, CH2Cl2, r.t. 30 min, 47%
HOO
HOAcO OH H OH
(+)-14-deacetyl eurylene
Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch
Total Synthesis of (—)-Spirotryprostatin B and Three Stereoisomers;Overman, L. E.; Rosen, D. M. Angew. Chem. Int. Ed. 2000, 39(24), 4596 - 4599
NSEM
O
N
NH
O
O
MeOON
SEMI
NH
N
O
OH
NSEM
O
NH
NH
O
O
MeOPdL2I
[Pd2(dba)3].CHCl3(otol)3P, KOAc
THF, 70 °C72% 1:1
12Kalesse & Gaich Seminar
NSEM
O
N
NH
O
O
MeO
Me2AlCl, i-Pr2NEt
NH
O
N
NH
O
O
MeO
( )-Spirotyprostatin B 1 : 1
Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch
PMBO
O O
PhSe
(a) NaIO4, NaHCO3, MeOH/H2O, 20 °C, 2 h(b) DBU, CH2=C(OMe)OTBS, Xylenes, refl., 6 h
O
O
Me
PMBO Me
Me
Total Synthesis of the Antimicrotubule Agent (+)-Discodermolide Using Boron-Mediated Aldol Reactions;Paterson, I.; Florence, G. J.; Gerlach, K.; Scott, J. P. Angew. Chem. Int. Ed. 2000, 39(2), 377- 380
13Kalesse & Gaich Seminar
OO
OH
HO
OH
OH O
NH2
O
(+) Discodermolide
OO
Me
PMBO Me
Me
O
O
Me
PMBO
Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch
A Stereoselective Total Synthesis of Zaragozic Acid A based on an Acetal [1,2] Wittig Rearrangement;Tomooka, K.; Kikuchi, M.; Igawa, K.; Suzuki, M.; Keong, P.-H.; Nakai, T. Angew. Chem. Int. Ed. 2000, 39(24), 4502 - 4505
14Kalesse & Gaich Seminar
Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch
Asymmetric Synthesis of Phorboxazole B – Part I: Synthesis of the C20-C38 and C39-C46 Subunits;Evans, D. A.; Cee, V. J.; Smith, T. E.; Fitch, D. M., Cho, P. S. Angew. Chem. Int. Ed. 2000, 39(14), 2533 - 2536
15Kalesse & Gaich Seminar
ON
O
HO
O
OO
O
N
OO
OH
MeO
Br
HOMeO
Phorboxazole B
Entry Phosphonate Yield Z : E
1 94 1.6 : 1
Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch
Total Synthesis of Bryostatin 3;Nishiyama, S.; Yamamura, S.; Ohmori, K.; Ogawa, Y.; Obitsu, T.; Ishikawa, Y. Angew. Chem. Int. Ed. 2000, 39(13), 2290 - 2294
H
MeO C
HOOAc
2 90 2.0 : 1
3 92 4.0 : 1
4 85 2.3 : 1
16Kalesse & Gaich Seminar
O O
O O
OO
n-Pr
HMeO2C
H
OH
O
OH
H
O
OH
O
Bryostatin 3
Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch
Highly diastereoselective Synthesis of Monocyclic and Bicyclic Secondary Diorganozinc Reagents with defined Configuration;Knochel, P.; Boudier, E.; Hupe, E. Angew. Chem. Int. Ed. 2000, 39(13), 2294 - 2997
17Kalesse & Gaich Seminar
Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch
18Kalesse & Gaich Seminar
Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch
Entry R a Yield [%] ee [%] b
1 96 81
2 83 93
A Chiral, Nonracemic Enolate with Dynamic Axial Chirality: Direct Asymmetric α-Methylation of α-Amino Acid Derivatives;Kawabata, T.; Suzuki, H.; Nagae, Y.; Fuji, K. Angew. Chem. Int. Ed. 2000, 39(12), 2155 - 2157
19Kalesse & Gaich Seminar
3 94 79
4 95 80
5 88 76
6 81 87
7 78 78
aee value for each substrate was >99 %; b determined by HPLC using columns with chiral stationary phase
Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch
Entry R1 R2 Yield [%]a
1 Me t-C H 97 (100)
The catalytic Alkylation of Aromatic Imines by Wilkinson's Complex: The Domino Reaction of Hydroacylation and ortho-Alkylation
Jun, C-H.; Hong, J-B.; Kim, Y-H.; Chung, K-Y. Angew. Chem. Int. Ed. 2000, 39(19), 3440 - 3442
20Kalesse & Gaich Seminar
1 Me t-C4H9 97 (100)
2 Me C6F5 91 (100)
3 Me Cy 65 (68)
4 Me n-C4H9 94 (97)b
7 Me TMS 92 (96)
9 Me 42 (47)c
10 Me 35
11 Et TMS 93 (100)d
12 n-C5H11 TMS 73(80)e
a GC yields are given in parentheses; b 5.0 equiv of olefin were used; c 3.0 equiv of olefin were
used; d 12% of di-ortho alkylation included; e 16% of di-ortho alkylation included
Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch
21Kalesse & Gaich Seminar
Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch
Entry Alcohol Anhydride / equiv Mol% cat. Time [h] Yield [%]
1 Ac2O / 10 3.0 1 96a
2 Ac2O / 10 0.5 7 95b
Highly Efficient and Versatile Acylation of Alcohols and Bi(OTf)3Otera, J.; Orita, A.; Tanahashi, C.; Kakuda, A. Angew. Chem. Int. Ed. 2000, 39(16), 2877 - 2879
22Kalesse & Gaich Seminar
3(PhCO) 2O / 0.5
(t-BuCO)2O / 3.0
3.0
3.0
8
4
2c
99
4 (PhCO) 2O / 5.0 3.0 48 0c
5 (PhCO) 2O / 1.5 3.0 24 90c
6 1-adamatol (t-BuCO)2O / 1.5 3.0 4 94
7 (t-BuCO)2O / 1.5 3.0 4 97
a MeCN used as solvent; b THF used as solvent; c determined by GC
Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch
Entry R Rh : Ligand Mol% Rh Conversion [%] ee [%]
1 Me 1 : 1 0.1 100 89.2
2 i-Pr 1 : 1 0.1 100 97.6
3 Ph 1 : 1 0.1 100 96.6
4 o-Br-Ph 1 : 1 0.1 100 89.8
Highly enantioselective Rh-Catalyzed Hydrogenation Reactions based on Chiral Monophosphite LigandsReetz, M.T.; Mehler, G. Angew. Chem. Int. Ed. 2000, 39(21), 3889 - 3890
23Kalesse & Gaich Seminar
5 2,6-(Me)2-Ph 1 : 1 0.1 78 39.2
6 2,6-(Ph)2-Ph 1 : 1 0.1 8 28.6
7 (R)-2-(1-phenylethyl) 1 : 1 0.1 100 99.2
8 (S)-2-(1-phenylethyl) 1 : 1 0.1 100 98.2
9 (R)-2-(1-phenylethyl) 1 : 1 0.04 100 99.4
10 (R)-2-(1-phenylethyl) 1 : 1 0.02 100 99.4
11 (R)-2-(1-phenylethyl) 1 : 1 0.01 49 96.2
12 (R)-2-(1-phenylethyl) 1 : 2 0.1 100 99.6
13 (R)-2-(1-phenylethyl) 1 : 4 0.1 100 99.5
14 (R/S)-2-(1-phenylethyl) 1 : 1 0.1 100 98.8
Ph
Me
Ph
Me
(S)-2-(1-phenylethyl)
(R)-2-(1-phenylethyl)
Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch
Syntheses not covered
O
O
H
H
S
NH
OOH
OOH
Epithilone B
Shibasaki, M.; Sawada, D.;Angew. Chem. Int. Ed. 2000, 39(1), 209 - 213
O
HO
O
OH
OHO O
(+)-Ratjadone
Kalesse, M.; Christmann, M.; Bhatt, U.; Quitschalle, E. C.;Angew. Chem. Int. Ed. 2000, 39(23), 4364 - 4366
24Kalesse & Gaich Seminar
Frondosin B
Danishefsky, S. J.; Inoue, M.; Frontier, A. J.Angew. Chem. Int. Ed. 2000, 39(4), 761 - 764