RSS-Feed abonnieren
DOI: 10.1055/s-0030-1258424
Synthesis of Catalytically Active Ruthenium Complexes with a Remote Chiral Lactam as Hydrogen-Bonding Motif
Publikationsverlauf
Publikationsdatum:
08. Februar 2011 (online)
Abstract
A terminal alkyne was prepared, which is linked by a carbon-carbon bond to a conformationally restricted, U-shaped chiral lactam, that is, more precisely, to carbon atom C7 of 1,5,7-trimethyl-3-azabicyclo[3.3.1]nonan-2-one. The alkyne was connected to various ligands (bipyridine, terpyridine, pybox) by Sonogashira cross-coupling with the respective bromides or triflates. The resulting products were converted into four defined ruthenium complexes (58-94% yield). The complexes contain a catalytically active metal center, which is spatially remote from the hydrogen-bonding motif of the chiral lactam. Preliminary experiments with one of these complexes proved that the complex shows catalytic activity in oxidation reactions and that enantioselectivity is achieved due to substrate coordination to the chiral lactam.
Key words
supramolecular chemistry - hydrogen bonds - catalysis - coordination chemistry - cross-coupling reactions
-
3a
Hartwig J. Organotransition Metal Catalysis: From Bonding to Catalysis University Science Books; Sausalito: 2010. -
3b
Walsh PJ.Kozlowski MC. Fundamentals of Asymmetric Catalysis University Science Books; Sausalito: 2009. -
3c
Catalytic
Asymmetric Synthesis
2nd ed.:
Ojima I. Wiley-VCH; New York: 2000. - For selective oxidation reactions achieved by combining a noncovalent binding site with a catalytically active metal, see:
-
4a
Breslow R.Zhang X.Huang Y. J. Am. Chem. Soc. 1997, 119: 4535 -
4b
Yang J.Breslow R. Angew. Chem. Int. Ed. 2000, 39: 2692 -
4c
Fang Z.Breslow R. Org. Lett. 2006, 8: 251 -
4d
Das S.Incarvito CD.Crabtree RH.Brudvig GW. Science 2006, 312: 1941 -
4e
Das S.Brudvig GW.Crabtree RH. J. Am. Chem. Soc. 2008, 130: 1628 -
4f
Lee SJ.Cho S.-H.Mulfort KL.Tiede DM.Hupp JT.Nguyen ST. J. Am. Chem. Soc. 2008, 130: 16828 -
4g
Hull JF.Sauer ELO.Incarvito CD.Faller JW.Brudvig GW.Crabtree RH. Inorg. Chem. 2009, 48: 488 - For artificial metalloenzymes, which act by tethering a transition metal to a host protein via hydrogen bonds, see:
-
5a
Letondor C.Humbert N.Ward TR. Proc. Natl. Acad. Sci. U.S.A. 2005, 102: 4683 -
5b
Pordea A.Creus M.Panek J.Duboc C.Mathis D.Novic M.Ward TR. J. Am. Chem. Soc. 2008, 130: 8085 ; and references cited therein -
6a
Fackler P.Berthold C.Voss F.Bach T. J. Am. Chem. Soc. 2010, 132: 15911 -
6b
Voss F.Herdtweck E.Bach T. Chem. Commun. 2011, 47: in press; DOI: 10.1039/C0CC04636A - 7
Voss F.Bach T. Synlett 2010, 1493 - 8
Sonogashira K.Tohda Y.Hagihara N. Tetrahedron Lett. 1975, 4467 - 9
Faraoni R.Blanzat M.Kubicek S.Braun C.Schweizer WB.Gramlich V.Diederich F. Org. Biomol. Chem. 2004, 2: 1962 - 10
Akiyama T.Nishimoto H.Ozaki S. Bull. Chem. Soc. Jpn. 1990, 63: 3356 -
11a
Ohira S. Synth. Commun. 1989, 19: 561 -
11b
Müller S.Liepold B.Roth GJ.Bestmann HJ. Synlett 1996, 521 -
12a
Stack JG.Curran DP.Geib SV.Rebek J.Ballester P. J. Am. Chem. Soc. 1992, 114: 7007 -
12b
Bach T.Bergmann H.Grosch B.Harms K.Herdtweck E. Synthesis 2001, 1395 - 13 For related cyclization reactions
of acyloxyiminium ions, see:
Hanessian S.Tremblay M.Marzi M.Del Valle JR. J. Org. Chem. 2005, 70: 5070 ; and references cited therein - 14 For related intramolecular Friedel-Crafts
reactions, see:
Zubkov FI.Boltukhina EV.Turchin KF.Borisov RS.Varlamov AV. Tetrahedron 2005, 61: 4099 ; and references cited therein - 15
Huang QP.Guo ZQ.Ruan YP. Org. Lett. 2006, 8: 1435 -
16a
Juris A.Balzani V.Barigelletti F.Campagna S.Belser P.von Zelewsky A. Coord. Chem. Rev. 1988, 84: 85 -
16b
Sauvage JP.Collin JP.Chambron JC.Guillerez S.Coudret C.Balzani V.Barigelletti F.De Cola L.Flamigni L. Chem. Rev. 1994, 94: 993 - 17
Potts KT.Konwar D. J. Org. Chem. 1991, 56: 4815 - 18
Thorand S.Krause N. J. Org. Chem. 1998, 63: 8551 -
19a
APEX Suite of Crystallographic Software. APEX
2 Version 2008.4
Bruker AXS Inc.;
Madison
USA:
2008.
-
19b
SAINT,
Version 7.56a and SADABS Version 2008/1
Bruker
AXS Inc.;
Madison USA:
2008.
-
19c Sir92 Program:
Altomare A.Cascarano G.Giacovazzo C.Guagliardi A.Burla MC.Polidori G.Camalli M. J. Appl. Crystallogr. 1994, 27: 435 -
19d
International
Tables for Crystallography
Vol. C:
Wilson AJC. Kluwer Academic Publishers; Dordrecht: 1992. -
19e
Sheldrick GM. Shelxl-97 Universität Göttingen; Germany: 1998. -
19f
Spek AL.Platon A. Multipurpose Crystallographic Tool Utrecht University; The Netherlands: 2010. -
19g WinGX, Version 1.70.01
January 2005:
Farrugia LJ. J. Appl. Crystallogr. 1999, 32: 837 -
19h
CCDC 806407 (13) contains the supplementary crystallographic data for this paper. They can be obtained free of charge from The Cambridge Crystallographic Data Centre: www.ccdc.cam.ac.uk/data_request/cif.
- 20
Winter A.Hummel J.Risch N. J. Org. Chem. 2006, 71: 4862 - 21
Campagna S.Puntoriero F.Nastasi F.Bergamini G.Balzani V. Top. Curr. Chem. 2007, 280: 117 - 22
Nishiyama H.Shimada T.Itoh H.Sugiyama H.Motoyama Y. Chem. Commun. 1997, 1863 -
23a
Tse MK.Bhor S.Klawonn M.Döbler C.Beller M. Tetrahedron Lett. 2003, 44: 7479 -
23b
Klawonn M.Tse MK.Bhor S.Döbler C.Beller M. J. Mol. Catal. A: Chem. 2004, 218: 13 -
23c
Bhor S.Tse MK.Klawonn M.Döbler C.Mägerlein W.Beller M. Adv. Synth. Catal. 2004, 346: 263 -
23d
Tse MK.Döbler C.Bhor S.Klawonn M.Mägerlein W.Hugl H.Beller M. Angew. Chem. Int. Ed. 2004, 43: 5255 -
23e
Tse MK.Klawonn M.Bhor S.Döbler C.Anilkumar G.Hugl H.Mägerlein W.Beller M. Org. Lett. 2005, 7: 987 - 24
Brotschi C.Mathis G.Leumann CJ. Chem. Eur. J. 2005, 11: 1911 - 25
Chaignon F.Torroba J.Blart E.Borgström M.Hammarström L.Odobel F. New J. Chem. 2005, 29: 1272 - 26
de Bettencourt-Dias A.Viswanathan S.Rollett A. J. Am. Chem. Soc. 2007, 129: 15436 - Examples for enantioselective photochemical and radical reactions of quinolones, mediated or catalyzed by chiral 1,5,7-trimethyl-3-azabicyclo[3.3.1]nonan-2-ones:
-
27a
Bach T.Bergmann H.Harms K. Angew. Chem. Int. Ed. 2000, 39: 2302 -
27b
Bach T.Bergmann H.Grosch B.Harms K. J. Am. Chem. Soc. 2002, 124: 7982 -
27c
Bauer A.Westkämper F.Grimme S.Bach T. Nature 2005, 436: 1139 -
27d
Dressel M.Bach T. Org. Lett. 2006, 8: 3145 -
27e
Müller C.Bauer A.Bach T. Angew. Chem. Int. Ed. 2009, 48: 6640 -
27f
Selig P.Herdtweck E.Bach T. Chem. Eur. J. 2009, 15: 3509 -
28a
Suzuki A. J. Organomet. Chem. 1999, 576: 147 -
28b
Miyaura N.Suzuki A. Chem. Rev. 1995, 95: 2457 - 29
Sabol MR.Owen JM.Erickson WR. Synth. Commun. 2000, 30: 427 - 30
Fairlamb IJS.Marrison LR.Dickinson JM.Lu F.-J.Schmidt JP. Bioorg. Med. Chem. 2004, 12: 4285 - 31
Gottlieb HE.Kotlyar V.Nudelman A. J. Org. Chem. 1997, 62: 7512 - 32
Bauer A.Bach T. Tetrahedron: Asymmetry 2004, 15: 3799 - 33
Sullivan BP.Calvert JM.Meyer TJ. Inorg. Chem. 1980, 19: 1404 - 34
Marmion ME.Takeuchi KJ. J. Am. Chem. Soc. 1988, 110: 1472
References
Current address: Novartis Pharma AG, Novartis Campus, 4056 Basel, Switzerland.
2Current address: Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA.