RSS-Feed abonnieren
DOI: 10.1055/s-0029-1218374
A Chiral Bifunctional Sulfonamide as an Organocatalyst: Alcoholysis of σ-Symmetric Cyclic Dicarboxylic Anhydrides
Publikationsverlauf
Publikationsdatum:
18. November 2009 (online)

Abstract
Enantioselective alcoholysis of σ-symmetric cyclic dicarboxylic anhydrides with benzyl alcohol catalyzed by a chiral bifunctional sulfonamide was achieved in up to 98% ee at 5 mol% loading.
Key words
anhydrides - asymmetric synthesis - homogeneous catalysis - sulfonamides - alcoholysis
- Supporting Information for this article is available online:
- Supporting Information
- For recent reviews on enzymes in organic chemistry, see:
- 1a
Suga T. Curr. Org. Chem. 1999, 3: 377 - 1b
Koeller KM.Wong C.-H. Nature (London) 2001, 409: 232 - 1c
Sheldon RA.van Rantwijk F. Aust. J. Chem. 2004, 57: 281 - 1d
Sureshkumar M.Lee C.-K. J. Mol. Catal. B: Enzym. 2009, 60: 1 - For recent reviews on organocatalysts, see:
- 2a
Ooi T.Maruoka K. Acc. Chem. Res. 2004, 37: 526 - 2b
Tian S.-K.Chen Y.Hang J.Tang L.McDaid P.Deng L. Acc. Chem. Res. 2004, 37: 621 - 2c
Kobayashi S.Sugiura M.Ogawa C. Adv. Synth. Catal. 2004, 346: 1023 - 2d
Dalko PI.Moisan L. Angew. Chem. Int. Ed. 2004, 43: 5138 - 2e
Dalaigh CO. Synlett 2005, 875 - 2f
Gaunt MJ.Johansson CCC.McNally A.Vo NT. Drug Discovery Today 2006, 12: 8 - 2g
Lelais G.MacMillan DWC. Aldrichimica Acta 2006, 39: 79 - 2h
Imada Y.Naota T. Chem. Rec. 2007, 7: 354 - 2i
Buckley BR. Annu. Rep. Prog. Chem., Sect. B: Org. Chem. 2007, 103: 90 - 2j
McGarrigle EM.Myers EL.Illa O.Shaw MA.Riches SL.Aggarwal VK. Chem. Rev. 2007, 107: 5841 - 2k
Guillena G.Najera C.Ramon DJ. Tetrahedron: Asymmetry 2007, 18: 2249 - 2l
Marion N.Díez-González S.Nolan SP. Angew. Chem. Int. Ed. 2007, 46: 2988 - 2m
You S.-L. Chem. Asian J. 2007, 2: 820 - 2n
Renaud P.Leong P. Science 2008, 322: 55 - 2o
MacMillan DWC. Nature (London) 2008, 455: 304 - 2p
Barbas CF. Angew. Chem. Int. Ed. 2008, 47: 42 - 2q
Chen Y.-C. Synlett 2008, 1919 - 2r
Gruttadauria M.Giacalone F.Noto R. Chem. Soc. Rev. 2008, 37: 1666 - 2s
Xu L.-W.Luo J.Lu Y. Chem. Commun. 2009, 1807 - 2t
Yoshioka E.Kohtani S.Miyabe H. Heterocycles 2009, 79: 229 - 2u
Connon SJ. Synlett 2009, 354 - For reviews on desymmetrization of cyclic anhydrides, see:
- 3a
Spivey AC.Andrews BI. Angew. Chem. Int. Ed. 2001, 40: 3131 - 3b
Chen Y.McDaid P.Deng L. Chem. Rev. 2003, 103: 2965 - 3c
Atodiresei I.Schiffers I.Bolm C. Chem. Rev. 2007, 107: 5683 - 4a
Rho HS.Oh SH.Lee JW.Lee JY.Chin J.Song CE. Chem. Commun. 2008, 1208 - 4b
Oh SH.Rho HS.Lee JW.Lee JE.Youk SH.Chin J.Song CE. Angew. Chem. Int. Ed. 2008, 47: 7872 - 5
Peschiulli A.Gun’ko Y.Connon SJ. J. Org. Chem. 2008, 73: 2454 - 6
Wang S.-X.Chen F.-E. Adv. Synth. Catal. 2009, 351: 547 - 7
Honjo T.Sano S.Shiro M.Nagao Y. Angew. Chem. Int. Ed. 2005, 44: 5838 - 8a
Henderson R. J. Mol. Biol. 1970, 54: 341 - 8b
Perona JJ.Craik CS. Protein Sci. 1995, 4: 337 - 8c
Perona JJ.Craik CS. J. Biol. Chem. 1997, 272: 29987 - 8d
Silverman RB. In The Organic Chemistry of Enzyme-Catalyzed Reactions Academic Press; San Diego: 2000. p.39 - 8e
Malthouse JPG. Biochem. Soc. Trans. 2007, 35: 566 - 10
Zhu L.-M.Tedford MC. Tetrahedron 1990, 46: 6587 - 12
Yamaguchi K. J. Mass Spectrom. 2003, 38: 473 - 13
Yu X.Wang W. Chem. Asian J. 2008, 3: 516
References and Notes
General Experimental
Procedure for Chiral Sulfonamide 1 Catalyzed Alcoholysis of Cyclic Dicarboxylic
Anhydrides
To a solution of 3-phenylglutaric anhydride
(2a, 190 mg, 1.0 mmol) and chiral sulfonamide 1 (25.8 mg, 0.05 mmol) in Et2O
(10 mL) was added BnOH (125 µL, 1.2 mmol) at r.t. After
stirring at r.t. for 20 h, the reaction mixture was treated with
10% HCl followed by extraction with CHCl3. The extract
was dried over anhyd MgSO4, filtered, and concentrated
in vacuo. To a solution of the residue in benzene-MeOH
(7:2, 9 mL) was added a solution of TMSCHN2 (2.0 M in
Et2O, 1 mL, 2.0 mmol). After being stirred at r.t. for
15 min, the reaction mixture was evaporated in vacuo. The oily residue
was purified by silica gel column chromatography [EtOAc-n-hexane (1:4)] to afford methyl ester
(S)-4a (286
mg, 92% yield, 87% ee) as a colorless oil. The
ee (%) of (S)-4a was
determined on a Chiralpak AD-H column [Daicel, eluent: n-hexane-2-PrOH (15:1), flow
rate: 1 mL/min, detection: 254 nm]. The retention
times were 12.5 min [minor isomer, (R)-4a] and 13.8 min [major
isomer, (S)-4a],
respectively. The absolute configuration of (S)-4a was explicitly determined by its chemical
conversion to thioester (S)-5 (Scheme
[¹]
).
[7]

Scheme1
For details see Supporting Information.