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DOI: 10.1055/s-0029-1217758
Lappaconitine-Catalyzed Asymmetric α-Hydroxylation of β-Keto Esters: A Brønsted Base Organocatalyst Developed from Terpenoid Alkaloids
Publikationsverlauf
Publikationsdatum:
04. September 2009 (online)
Abstract
Discovering organocatalysts with novel framework from terpenoid alkaloids is presented in this paper. Lappaconitine was found to enantioselectively catalyze α-hydroxylation of β-keto esters using tert-butyl hydroperoxide as the oxidant in chloroform to afford the corresponding products in high yields and good enantioselectivity (up to 85% ee).
Key words
lappaconitine - asymmetric α-hydroxylation - β-keto esters - organocatalyst - terpenoid alkaloid
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- Supporting Information
- For the reviews, see:
-
1a
Dalko PI.Moisan L. Angew. Chem. Int. Ed. 2004, 43: 5138 -
1b
List B.Seayad J. Org. Biomol. Chem. 2005, 3: 719 -
1c
List B.Yang JW. Science 2006, 313: 1584 -
1d
Helene P. Tetrahedron 2007, 63: 9267 -
1e
Dondoni A.Massi A. Angew. Chem. Int. Ed. 2008, 47: 2 -
1f
Barbas CF. Angew. Chem. Int. Ed. 2008, 47: 42 -
1g
Melchiorre P.Marigo M.Carlone A.Bartoli G. Angew. Chem. Int. Ed. 2008, 47: 6138 -
1h
MacMillan DWC. Nature (London) 2008, 455: 304 -
2a
Adamo Mauro FA.Aggarwal VK.Sage MA. J. Am. Chem. Soc. 2000, 122: 8317 -
2b
Brown SP.Brochu MP.Sinz CJ.MacMillan DWC. J. Am. Chem. Soc. 2003, 125: 10808 -
2c
Zhong GF. Angew. Chem. Int. Ed. 2003, 42: 4247 -
2d
Hayashi Y.Yamaguchi J.Hibino K.Shoji M. Tetrahedron Lett. 2003, 44: 8293 -
2e
Sunden H.Engqvist M.Casas J.Ibrahem I.Cordova A. Angew. Chem. Int. Ed. 2004, 43: 6532 -
2f
Lattanzi A. Org. Lett. 2005, 7: 2579 -
2g
Marigo M.Franzen J.Poulsen TB.Zhuang W.Jorgensen KA. J. Am. Chem. Soc. 2005, 127: 6964 -
2h
Ho CY.Chen YC.Wong MK.Yang D. J. Org. Chem. 2005, 70: 898 -
2i
Russo A.Lattanzi A. Adv. Synth. Catal. 2008, 350: 1991 -
2j
Lu M.Zhu D.Hou YX.Tan B.Zhong GF. Angew. Chem. Int. Ed. 2008, 47: 10187 -
3a
Julia S.Masana J.Vega JC. Angew. Chem., Int. Ed. Engl. 1980, 19: 929 -
3b
Bentley PA.Roberts SM. Chem. Commun. 1997, 739 -
3c
Gerlach A.Geller T. Adv. Synth. Catal. 2004, 346: 1247 -
3d
Pedrosa LJM.Pitts MR.Roberts SM. Tetrahedron Lett. 2004, 45: 5073 -
3e
Berkessel A. Angew. Chem. Int. Ed. 2008, 47: 3677 -
4a
Taylor EG, andWilmington DD. inventors; WO 03/040083. ; Chem. Abstr. 2003, 138, 385179 -
4b For using the cinchona alkaloids
derivatives as the phase-transfer catalysts in the transformation
of carbon-hydrogen bond to carbon-oxygen bond,
see:
Acocella MR.Mancheno OG.Bella M.Jørgensen KA. J. Org. Chem. 2004, 69: 8165 -
4c
Daisuke S.Kazuhiro N.Takashi I. Org. Lett. 2008, 10: 1593 -
4d
Moriyasu M.Akira A.Takayuki S. Tetrahedron Lett. 1988, 29: 2835 -
5a
Shi Y. Acc. Chem. Res. 2004, 37: 488 -
5b
Yang D. Acc. Chem. Res. 2004, 37: 497 -
5c
Armstrong A.Ahmed G.Fernandez BD.Hayter BR.Wailes JS. J. Org. Chem. 2002, 67: 8610 -
5d
Wang B.Wong OA.Zhao MX.Shi Y. J. Org. Chem. 2008, 73: 9539 -
6a
Page PCB.Buckley B.Blaker J. Org. Lett. 2004, 6: 1543 -
6b
Page PCB.Barros D.Buckley BR.Ardakani A.Marples BA. J. Org. Chem. 2004, 69: 3595 -
6c
Page PCB.Buckley BR.Heaney H.Blacker AJ. Org. Lett. 2005, 7: 375 -
6d
Page PCB.Barros D.Buckley BR.Marples BA. Tetrahedron: Asymmetry 2005, 16: 3488 -
6e
Page PCB.Buckley BR.Barros D.Blacker AJ.Marples BA.Elsegood MRJ. Tetrahedron 2007, 63: 5386 -
7a
Soai K.Niwa S. Chem. Rev. 1992, 92: 833 -
7b
Boyall D.Lopez F.Sasaki H.Frantz D.Carreira EM. Org. Lett. 2000, 2: 4233 -
8a Institute
of Plant in Chinese Academy of Sciences,
China
Higher Plant Illustrated Handbook
Vol. 2:
Science;
Beijing:
1992.
p.531
-
8b
Tang XC.Zhu MY.Feng J.Wang YE. Acta Pharmacologica Sinica 1983, 18: 579 -
8c
Mollov N.Tada M.Marion L. Tetrahedron Lett. 1969, 26: 2189 -
8d
Birnbaum GI. Tetrahedron Lett. 1969, 26: 2193 -
8e
Turdybekov DM.Turdybekov KM.Burdelnaya EV.Turmukhambetov AZ.Adekenov SM.Gatilov YV. Chem. Nat. Compd. 2003, 39: 19 -
8f
Zhang J.Sun XW.Wen HH.Liu HS.Li HK.Yu KB.Wang YP. Chin. J. Org. Chem. 2007, 27: 1409 -
8g
Polyakov NE.Leshina TV. Russ. Chem. Bull. 2007, 56: 631 - 9
Christoffers J.Baro A.Werner T. Adv. Synth. Catal. 2004, 346: 143 -
10a
Toullec PY.Bonaccorsi C.Mezzetti A.Togni A. Proc. Natl. Acad. Sci. U.S.A. 2004, 101: 5810 -
10b
Bonaccorsi C.Althaus M.Becker C.Togni A.Mezzetti A. Pure Appl. Chem. 2006, 78: 391 -
10c
Ishimaru T.Shibata N.Nagai J.Nakamura S.Toru T.Kanemasa S. J. Am. Chem. Soc. 2006, 128: 16488 - 11
Lu M.Zhu D.Lu YP.Zeng XF.Tan B.Xu ZJ.Zhong GF. J. Am. Chem. Soc. 2009, 131: 4562
References and Notes
General Procedure
for Lappaconitine-Catalyzed Asymmetric α-Hydroxylation
of β-Keto Esters
A mixture of β-keto
ester (1 mmol), tert-butyl hydroperoxide
(5 mmol), lappaconitine (0.1 mmol) in CHCl3 (6 mL) was
stirred for 72 h at 15 ˚C. The reaction was monitored by
TLC. After the starting material vanished, the mixture was washed
with 10 wt% Na2SO3 and extracted
with CH2Cl2. The organic layer was then dried
over anhyd Na2SO4, filtered, and evaporated.
The residue was purified by flash chromatography (n-hexane-EtOAc = 3:1)
to give the product. The ee value was determined by chiral HPLC
on CHIRALCEL OD-H or AD-H column (hexane-i-PrOH = 90:10,
flow rate 1.0 mL/min, 254 nm, unless noted). See Supporting
Information for data of all compounds.