Highly Enantioselective Friedel–Crafts Reaction of Indole with Alkylidenemalonates Catalyzed by Heteroarylidene Malonate‐Derived Bis(oxazoline) Copper(II) Complexes

A series of cheap and easily accessible heteroarylidenemalonate-derived bis(oxazoline) ligands 1 and 2 were synthesized and their copper(II) complexes were applied to the catalytic Friedel-Crafts reaction between indoles and diethyl alkylidenemalonates, Excellent asymmetric enantioselectivities were afforded for the S-enantiomer (up to > 99% ee) in isobutyl alcohol, and the R-enantiomer (up to 96.5% ee) in dichloromethane.

[1]  K. Jiang,et al.  Chemoselective asymmetric N-allylic alkylation of indoles with Morita-Baylis-Hillman carbonates. , 2009, Angewandte Chemie.

[2]  G. Roelfes,et al.  Enantioselective Friedel-Crafts reactions in water using a DNA-based catalyst. , 2009, Angewandte Chemie.

[3]  Q. Kang,et al.  Asymmetric Friedel-Crafts reaction of 4,7-dihydroindoles with nitroolefins by chiral Brønsted acids under low catalyst loading. , 2009, Chemistry.

[4]  Xiaoming Feng,et al.  Enantioselective Friedel-Crafts alkylation of indoles with alkylidene malonates catalyzed by N,N'-dioxide-scandium(III) complexes: asymmetric synthesis of beta-carbolines. , 2009, Chemistry.

[5]  M. Hager,et al.  Dependence of enantioselectivity on the ligand/metal ratio in the asymmetric Michael addition of indole to benzylidene malonates: electronic influence of substrates. , 2008, Chemistry.

[6]  D. Du,et al.  Asymmetric Friedel-Crafts alkylation of electron-rich N-heterocycles with nitroalkenes catalyzed by diphenylamine-tethered bis(oxazoline) and bis(thiazoline) Zn(II) complexes. , 2008, Chemistry, an Asian journal.

[7]  K. Jørgensen,et al.  Catalytic asymmetric Friedel-Crafts alkylation reactions--copper showed the way. , 2008, Chemical reviews.

[8]  Q. Kang,et al.  Highly enantioselective friedel-crafts reaction of 4,7-dihydroindoles with imines by chiral phosphoric acids: facile access to 2-indolyl methanamine derivatives. , 2008, Chemistry.

[9]  O. Reiser,et al.  Metal-bis(oxazoline) complexes: From coordination chemistry to asymmetric catalysis , 2008 .

[10]  Nuno M. M. Moura,et al.  Cu(I) catalysed cyclopropanation of olefins: Stereoselectivity studies with Arylid-Box and Isbut-Box ligands , 2007 .

[11]  Shou‐Fei Zhu,et al.  Chiral Brønsted acid catalyzed enantioselective Friedel-Crafts reaction of indoles and alpha-aryl enamides: construction of quaternary carbon atoms. , 2007, Angewandte Chemie.

[12]  Q. Kang,et al.  Highly enantioselective Friedel-Crafts reaction of indoles with imines by a chiral phosphoric acid. , 2007, Journal of the American Chemical Society.

[13]  K. Scheidt,et al.  Enantioselective Friedel-Crafts alkylations catalyzed by bis(oxazolinyl)pyridine-scandium(III) triflate complexes. , 2003, Journal of the American Chemical Society.

[14]  M. Hager,et al.  Highly enantioselective michael additions of indole to benzylidene malonate using simple bis(oxazoline) ligands: importance of metal/ligand ratio. , 2006, Organic letters.

[15]  Yong-Qiang Wang,et al.  Enantioselective Friedel-Crafts reaction of indoles with carbonyl compounds catalyzed by bifunctional cinchona alkaloids. , 2006, Organic letters.

[16]  G. Desimoni,et al.  C(2)-symmetric chiral bis(oxazoline) ligands in asymmetric catalysis. , 2006, Chemical reviews.

[17]  Nuno M. M. Moura,et al.  Arylid-Box: A new family of chiral bis-oxazoline ligands for metal mediated catalytic enantioselective synthesis , 2006 .

[18]  S. O’Connor,et al.  Chemistry and biology of monoterpene indole alkaloid biosynthesis. , 2006, Natural product reports.

[19]  Jun Song,et al.  Asymmetric Friedel-crafts reaction of indoles with imines by an organic catalyst. , 2006, Journal of the American Chemical Society.

[20]  K. Fandrick,et al.  Catalytic Enantioselective Pyrrole Alkylations of α,β-Unsaturated 2-Acyl Imidazoles , 2006 .

[21]  D. Du,et al.  Enantioselective Friedel-Crafts alkylation of indoles with nitroalkenes catalyzed by bifunctional tridentate bis(oxazoline)-Zn(II) complex. , 2006, Organic letters.

[22]  Qi‐Lin Zhou,et al.  Asymmetric Friedel-Crafts alkylations of indoles with nitroalkenes catalyzed by Zn(II)-bisoxazoline complexes. , 2006, The Journal of organic chemistry.

[23]  Raquel P. Herrera,et al.  Catalytic enantioselective Friedel-Crafts alkylation of indoles with nitroalkenes by using a simple thiourea organocatalyst. , 2005, Angewandte Chemie.

[24]  Jian Zhou,et al.  Modular synthesis of chiral homo- and heterotrisoxazolines. Improving the enantioselectivity in the asymmetric Michael addition of indole to benzylidene malonate. , 2005, The Journal of organic chemistry.

[25]  Davidr . Evans,et al.  Enantioselective Friedel-Crafts alkylations of alpha,beta-unsaturated 2-acyl imidazoles catalyzed by bis(oxazolinyl)pyridine-scandium(III) triflate complexes. , 2005, Journal of the American Chemical Society.

[26]  M. Bandini,et al.  A Journey Across Recent Advances in Catalytic and Stereoselective Alkylation of Indoles , 2005 .

[27]  Jian Zhou,et al.  Sidearm approach: a promising strategy for construction of bisoxazoline-based ligand library. , 2004, Journal of combinatorial chemistry.

[28]  Jian Zhou,et al.  Controllable enantioselective Friedel-Crafts reaction between indoles and alkylidene malonates catalyzed by pseudo-C3-symmetric trisoxazoline copperII complexes. , 2004, The Journal of organic chemistry.

[29]  M. Franzini,et al.  Toggling enantioselective catalysis--a promising paradigm in the development of more efficient and versatile enantioselective synthetic methodologies. , 2003, Chemical Society reviews.

[30]  D. Du,et al.  Novel chiral dibenzo[a,c]cycloheptadiene bis(oxazoline) and catalytic enantioselective cyclopropanation of styrene , 2003 .

[31]  Jian Zhou,et al.  Sidearm effect: improvement of the enantiomeric excess in the asymmetric Michael addition of indoles to alkylidene malonates. , 2002, Journal of the American Chemical Society.

[32]  K. Jørgensen,et al.  On the intermediates in chiral bis(oxazoline)copper(II)-catalyzed enantioselective reactions--experimental and theoretical investigations. , 2002, Chemistry.

[33]  D. MacMillan,et al.  Enantioselective organocatalytic indole alkylations. Design of a new and highly effective chiral amine for iminium catalysis. , 2002, Journal of the American Chemical Society.

[34]  M. Sibi,et al.  Reversal of Stereochemistry in Enantioselective Transformations. Can They Be Planned or Are They Just Accidental , 2001 .

[35]  K. Jørgensen,et al.  Catalytic Asymmetric Friedel-Crafts Alkylation of β,γ-Unsaturated α-Ketoesters: Enantioselective Addition of Aromatic C-H Bonds to Alkenes. , 2001, Angewandte Chemie.

[36]  Davidr . Evans,et al.  Enantioselective Lewis Acid Catalyzed Michael Reactions of Alkylidene Malonates. Catalysis by C2-Symmetric Bis(oxazoline) Copper(II) Complexes in the Synthesis of Chiral, Differentiated Glutarate Esters , 2000 .

[37]  Denmark.,et al.  Effect of ligand structure in the bisoxazoline mediated asymmetric addition of methyllithium to imines , 2000, The Journal of organic chemistry.

[38]  J. S. Johnson,et al.  Chiral bis(oxazoline) copper(II) complexes: versatile catalysts for enantioselective cycloaddition, Aldol, Michael, and carbonyl ene reactions. , 2000, Accounts of chemical research.

[39]  Scott J. Miller,et al.  CHIRAL BIS(OXAZOLINE)COPPER(II) COMPLEXES AS LEWIS ACID CATALYSTS FOR THE ENANTIOSELECTIVE DIELS-ALDER REACTION , 1999 .

[40]  Davidr . Evans,et al.  C2-SYMMETRIC CU(II) COMPLEXES AS CHIRAL LEWIS ACIDS. CATALYTIC ENANTIOSELECTIVE MICHAEL ADDITION OF SILYLKETENE ACETALS TO ALKYLIDENE MALONATES , 1999 .

[41]  Robert J. Deeth,et al.  A CLFSE/MM study on the role of ligand bite-angle in Cu(II)-catalyzed Diels-Alder reactions , 1999 .

[42]  J. Bosch,et al.  PREPARATION OF ENANTIOPURE 6-(3-INDOLYL)-2-PIPERIDONES AND CONJUGATE ADDITIONS TO A 3,4-DIDEHYDRO DERIVATIVE , 1997 .

[43]  C. Senanayake,et al.  THE INFLUENCE OF LIGAND BITE ANGLE ON THE ENANTIOSELECTIVITY OF COPPER(II)-CATALYSED DIELS-ALDER REACTIONS , 1996 .

[44]  J. Edwards,et al.  Preparation of Chiral Bisoxazolines: Observations on the Effect of Substituents , 1995 .

[45]  J. Bosch,et al.  A General Method for the Synthesis of Bridged Indole Alkaloids. Addition of Carbon Nucleophiles to N-Alkylpyridinium Salts , 1995 .

[46]  Ramesh Krishnamurti,et al.  1.8 – Friedel–Crafts Alkylations , 1991 .