cyclopropenes an accessible precursor to enantioenriched compounds lucie zimmerliterature meeting...
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Cyclopropenes
An Accessible Precursor to Enantioenriched Compounds
Lucie ZimmerLiterature Meeting December 1st 2009
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Cyclopropenes: Naturally Occuring Products
1-MethylcyclopropeneUsed as synthetic plant growth regulator
O
OH
O
Alutaceonic acid BAntithrombotic
OH
O
Malvalic acidFound in cottonseed oil
Me H
H H
Me
Me
iPrMe
HO
(23R)-23H-isocalysterol
Cyclopropenes: Biologically Active Compounds
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Cyclopropenes: Caracteristics
27.5 kcalmol-1 53.7 kcalmol-1
π caracter of the 3-membered ring
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Cyclopropenes: Caracteristics
27.5 kcalmol-1 53.7 kcalmol-1
+π caracter of the double bond
=very reactive especially towards πphilic transition metals
π caracter of the 3-membered ring
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1. Syntheses of cyclopropenes 1.1 “Racemic” syntheses 1.2 “Enantioselective” syntheses
2. Carbometallation 2.1 From enantioenriched cyclopropenes 2.2 From racemic cyclopropenes
3. Cycloadditions 3.1 Diels-Alder 3.2 (3+2) 3.3 Pauson-Kahn
4. Metathesis
Summary
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1. Syntheses of cyclopropenes 1.1 “Racemic” syntheses 1.2 “Enantioselective” syntheses
2. Carbometallation 2.1 From enantioenriched cyclopropenes 2.2 From racemic cyclopropenes
3. Cycloadditions 3.1 Diels-Alder 3.2 (3+2) 3.3 Pauson-Kahn
4. Metathesis
Summary
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Cyclopropenes: Large Scale Synthesis
1.1.1 From cyclopropanes
Bolesov’s method revisited by Rubin, M.; Gevorgyan, V. Synthesis 2004, 2004, 796-800.
52g
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Cyclopropenes: Large Scale Synthesis
1.1.2 From Alkynes
Rubin, M.; Gevorgyan, V. Synthesis 2004, 2004, 796-800.
•No conversion was observed using 6 and 7 in presence of Rh2(OAc)4
•10 and 12 are obtained in a 10:1 ratio
•12 untouched during the deprotection of 10
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Cyclopropenes: Enantioselective Synthesis
1.2.1 Kinetic resolution
Breslow, R.; Douek, M. J. Am. Chem. Soc. 1968, 90, 2698-2699.
HPh
p-MeOPh
COOHH
Ph
p-MeOPh
PhOcinchonine
PhLi
enantioenriched
Liao, L.-a.; Zhang, F.; Dmitrenko, O.; Bach, R. D.; Fox, J. M. J. Am. Chem. Soc. 2004, 126, 4490-4491.
Ph
COOHPh
1) 1- adamantoyl chloride2)
(1.0 equiv) THF, -98°C
(1.0 equiv.)3) TBAF
O
NOLi
O
NOLi
OTBS
Ph
Ph
Ph
PhO
N
O
NO O
OO
HO
91% yielddr >99.5:0.5
87% yielddr >99:1
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Cyclopropenes: Enantioselective Synthesis
N
Rh
COOMe
Rh
4
[Rh2(5R-mepy)4]
HN2CHCOOR'
Rh2(5R-MEPY)4
DCM
COOtBuH
H
COOd-MenthylH
H
COOd-MenthylH
H
COOEtH
H
MeO MeO
MeO
69% ee 78% ee
98% de
yield 43%-73%
43% de
MeO
OMe
1.2.2 First enantioselective synthesis
Significance of the diazoSignificance of the polarity of the diazo(e.g. hexyne, dimethylbutyne)
OEt
OEtN2CHCOOMe
OEtEtO
COOMeH
[Rh2(5S-mepy)4]2 mol%
CH2Cl2, rt
85%90% ee
Protopopova, M. N.; Doyle, M. P.; Müller, P.; Ene, D. J. Am. Chem. Soc. 1992, 114, 2755-2757.Imogaï, H.; Bernardinelli, G.; Gränicher, C.; Moran, M.; Rossier, J.-C.; Müller, P. Helv. Chim. Acta 1998, 81, 1754-1764.
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Cyclopropenes: Enantioselective Synthesis
RN2CHCOOEt
R
COOEtH
[Rh2(OAc)(dpti)3]0.5 mol%
CH2Cl2, rt
R = Pent, 90%, 95%eeR = tBu, 81%, 92%eeR = CH2OBn, 86%, 92%eeR = CH2Br, 62%, 95%eeR = CH2OCH2CH=CHC6H5, 76%, 95%ee
Lou, Y.; Horikawa, M.; Kloster, R. A.; Hawryluk, N. A.; Corey, E. J. J. Am. Chem. Soc. 2004, 126, 8916-8918.Lou, Y.; Remarchuk, T. P.; Corey, E. J. J. Am. Chem. Soc. 2005, 127, 14223-14230.
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Cyclopropenes: Enantioselective Synthesis
Quaternary center formation
Davies, H. M. L.; Lee, G. H. Org. Lett. 2004, 6, 1233-1236.
R
R
COOMePh
[Rh2(S-dosp)4]1 mol%
hexane, rt
R = Ph, 62%, 90%eeR = Bu, 54%, 84%ee
Ph COOMe
N2
N
SO2C6H4R
O
O
Rh
Rh
H
R = C12H25
4
[Rh2(S-dosp)4]
R1
R3R2
R4
R3R2
R1
R3R2
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Cyclopropenes: Enantioselective Synthesis
Marek, I.; Simaan, S.; Masarwa, A. Angew. Chem., Int. Ed. 2007, 46, 7364-7376.
R1
R3R2
R4
R3R2
R1
R3R2
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Cyclopropenes: Large Scale Synthesis
6
N O
O Rh
Rh
SO2Ar
Ar = p-tBuCH6H4
N
O
N
O
tBu tBu
1
N Rh
O Rh
COOMe4
2a
NH
COOiBu
Rh
O Rh
5
Cyclopropanation vs Cyclopropenation
Doyle, M. P.; Ene, D. G.; Peterson, C. S.; Lynch, V. Angew. Chem., Int. Ed. 1999, 38, 700-702.
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1. Syntheses of cyclopropenes 1.1 “Racemic” syntheses 1.2 “Enantioselective” syntheses
2. Carbometallation 2.1 From enantioenriched cyclopropenes 2.2 From racemic cyclopropenes
3. Cycloadditions 3.1 Diels-Alder 3.2 (3+2) 3.3 Pauson-Kahn
4. Metathesis
Summary
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Rubin, M.; Rubina, M.; Gevorgyan, V. Chem. Rev. 2007, 107, 3117-3179.
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Pr
HOMgCl
Et2O, rt
HO
Pr
67%
H. G. Richey, Jr., R. M. Bension, J. Org. Chem. 1980, 45, 5036.Nakamura, M.; Isobe, H.; Nakamura, E. Chem. Rev. 2003, 103, 1295-1326.Rubina, M.; Rubin, M.; Gevorgyan, V. J. Am. Chem. Soc. 2002, 124, 11566-11567.Rubina, M.; Rubin, M.; Gevorgyan, V. J. Am. Chem. Soc. 2003, 125, 7198-7199.Rubina, M.; Rubin, M.; Gevorgyan, V. J. Am. Chem. Soc. 2004, 126, 3688-3689.
• hydrostannylation• silastannylation• stannastanylation• hydroboration• carbocupration• hydrogenation...
Cyclopropenes: Carbometallation
Diastereo- and Enantioselective:
Key metalsRhPd
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Cyclopropenes: Carbometallation
Liao, L.-a.; Fox, J. M. J. Am. Chem. Soc. 2002, 124, 14322-14323.
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Cyclopropenes: Enantioselective Synthesis
Liu, X.; Fox, J. M. J. Am. Chem. Soc. 2006, 128, 5600-5601.
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Cyclopropenes: Enantioselective Synthesis
Liu, X.; Fox, J. M. J. Am. Chem. Soc. 2006, 128, 5600-5601.
MeMgCl sparged with air can be replaced by MeOH (1 équiv.)
Good yields
Excellent ees
1,2- and 1,2,3-trisubstitued cyclopropanes
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Cyclopropenes: Enantioselective Synthesis
Liu, X.; Fox, J. M. J. Am. Chem. Soc. 2006, 128, 5600-5601.
But only MethylGrignard lead to good enantioselectivities...
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Cyclopropenes: Carbometallation
Tarwade, V.; Liu, X.; Yan, N.; Fox, J. M. J. Am. Chem. Soc. 2009, 131, 5382-5383.
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Cyclopropenes: Carbometallation
Tarwade, V.; Liu, X.; Yan, N.; Fox, J. M. J. Am. Chem. Soc. 2009, 131, 5382-5383.
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Cyclopropenes: Enantio- Synthesis of Cyclopropanes
Sherrill, W. M.; Rubin, M. J. Am. Chem. Soc. 2008, 130, 13804-13809.
Entry R1 R2 R3 Yield dr (2:3)
1 Ph Me H 87 11:1
2 p-Cl-C6H4 Me H 71* 8:1
3 p-F-C6H4 Me H 91* 12:1
4 Ph CH2OMOM H 72 10:1
5 Ph CH2OAc H 75* 7:1
6 Ph COOMe H 90 1:1
7 COOMe Me H 64 24:1
8 CMe2OBn Me H 91 2 only
9 Ph Me Me 80* 7:1
R3
R2R1 Rh(CO)2acac
dppf (P*:Rh = 2:1)
H2/CO 1:1, 150 psi60 °C, PhMe
R2R1
R2R1
CHO CHO
R3R3
21 3
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Sherrill, W. M.; Rubin, M. J. Am. Chem. Soc. 2008, 130, 13804-13809.
Cyclopropenes: Enantio- Synthesis of Cyclopropanes
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Sherrill, W. M.; Rubin, M. J. Am. Chem. Soc. 2008, 130, 13804-13809.
Cyclopropenes: Enantio- Synthesis of Cyclopropanes
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Sherrill, W. M.; Rubin, M. J. Am. Chem. Soc. 2008, 130, 13804-13809.
Cyclopropenes: Enantio- Synthesis of Cyclopropanes
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1. Syntheses of cyclopropenes 1.1 “Racemic” syntheses 1.2 “Enantioselective” syntheses
2. Carbometallation 2.1 From enantioenriched cyclopropenes 2.2 From racemic cyclopropenes
3. Cycloadditions 3.1 Diels-Alder 3.2 (3+2) 3.3 Pauson-Kahn
4. Metathesis
Summary
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3.1 Diels-Alder
Cyclopropenes: Enantio-Synthesis of Cyclic Compounds
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Cortistatin A
Magnus, P.; Littich, R. Org. Lett. 2009, 11, 3938-3941.
Cyclopropenes: Enantio-Synthesis of Cyclic Compounds
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Cyclopropenes: Enantio-Synthesis of Cyclic Compounds
Endo kinetic preference seems to be eroded by the extremely exothermic relief
of the cyclopropenyl ring strain in the transition state
of the Diels Alder.
LaRochelle, R. W.; Trost, B. M.; Krepski, L. J. Org. Chem. 1971, 36, 1126–1136.Al Dulayymi, A. R.; Al Dulayymi, J. R.; Baird, M. S. Tetrahedron, 2000, 56, 1115–1125.Van Royen, L. A.; Mijngheer, R.; De Clercq, P. J. Tetrahedron 1985, 41, 4667–4680.
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Magnus, P.; Littich, R. Org. Lett. 2009, 11, 3938-3941.
Cyclopropenes: Enantio-Synthesis of Cyclic Compounds
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Magnus, P.; Littich, R. Org. Lett. 2009, 11, 3938-3941.
Cyclopropenes: Enantio-Synthesis of Cyclic Compounds
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3.2 Cycloaddition (3+2)
Cyclopropenes: Enantio-Synthesis of Cyclic Compounds
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Cyclopropenes: Enantio-Synthesis of Cyclic Compounds
DeAngelis, A.; Taylor, M. T.; Fox, J. M. J. Am. Chem. Soc. 2009, 131, 1101-1105.
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Cyclopropenes: Enantio-Synthesis of Cyclic Compounds
DeAngelis, A.; Taylor, M. T.; Fox, J. M. J. Am. Chem. Soc. 2009, 131, 1101-1105.
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3.3 Pauson-Kahn
Cyclopropenes: Enantio-Synthesis of Cyclic Compounds
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Cyclopropenes: Enantio-Synthesis of Cyclic Compounds
Pallerla, M. K.; Fox, J. M. Org. Lett. 2005, 7, 3593-3595.
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Cyclopropenes: Enantio-Synthesis of Cyclic Compounds
Pallerla, M. K.; Fox, J. M. Org. Lett. 2005, 7, 3593-3595.
Pallerla, M. K.; Yap, G. P. A.; Fox, J. M. J. Org. Chem. 2008, 73, 6137-6141.
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Cyclopropenes: Enantio-Synthesis of Cyclic Compounds
Total Synthesis of (–)-pentalene
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Cyclopropenes: Enantio-Synthesis of Cyclic Compounds
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Cyclopropenes: Enantio-Synthesis of Cyclic Compounds
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Cyclopropenes: Enantio-Synthesis of Cyclic Compounds
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1. Syntheses of cyclopropenes 1.1 “Racemic” syntheses 1.2 “Enantioselective” syntheses
2. Carbometallation 2.1 From enantioenriched cyclopropenes 2.2 From racemic cyclopropenes
3. Cycloadditions 3.1 Diels-Alder 3.2 (3+2) 3.3 Pauson-Kahn
4. Metathesis
Summary
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Cyclopropenes: Enantio- Synthesis of Aliphatic Compounds
Giudici, R. E.; Hoveyda, A. H. J. Am. Chem. Soc. 2007, 129, 3824-3825.
Van Veldhuizen, J. J.; Campbell, J. E.; Giudici, R. E.; Hoveyda, A. H. J. Am. Chem. Soc. 2005, 127, 6877-6882.
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Cyclopropenes: Enantio- Synthesis of Aliphatic Compounds
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Cyclopropenes: Enantio- Synthesis of Aliphatic Compounds
Van Veldhuizen, J. J.; Campbell, J. E.; Giudici, R. E.; Hoveyda, A. H. J. Am. Chem. Soc. 2005, 127, 6877-6882.
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Hoveyda, A. H.; Lombardi, P. J.; O'Brien, R. V.; Zhugralin, A. R. J. Am. Chem. Soc. 2009, 131, 8378-8379.
Cyclopropenes: Enantio- Synthesis of Aliphatic Compounds
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Hoveyda, A. H.; Lombardi, P. J.; O'Brien, R. V.; Zhugralin, A. R. J. Am. Chem. Soc. 2009, 131, 8378-8379.
Cyclopropenes: Enantio- Synthesis of Aliphatic Compounds
![Page 50: Cyclopropenes An Accessible Precursor to Enantioenriched Compounds Lucie ZimmerLiterature Meeting December 1st 2009](https://reader035.vdocuments.mx/reader035/viewer/2022070307/551b3c0c550346dd1a8b5412/html5/thumbnails/50.jpg)
Cyclopropenes: Enantio- Synthesis of Aliphatic Compounds
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Conclusion
Pro-chiral and enantioenrichied cyclopropenes are easily accessible.
Cyclopropenes are pretty stable reactive intermediates.
They react by their intracyclic double bond.
They can be used for the formation of cyclopropanes, engaged in various cycloaddition reactions as well as ring opening strategies.
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Rubin, M.; Rubina, M.; Gevorgyan, V. Chem. Rev. 2007, 107, 3117-3179.
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methylene and alhylidene derivatives
Rubin, M.; Rubina, M.; Gevorgyan, V. Chem. Rev. 2007, 107, 3117-3179.Marek, I.; Simaan, S.; Masarwa, A. Angew. Chem., Int. Ed. 2007, 46, 7364-7376.