Full-text resources of PSJD and other databases are now available in the new Library of Science.
Visit https://bibliotekanauki.pl

PL EN


Preferences help
enabled [disable] Abstract
Number of results
2015 | 2 | 1 |

Article title

Synthesis of novel chiral bithiophenebased
phosphine oxides as Lewis bases in
organocatalytic stereoselective reactions

Content

Title variants

Languages of publication

EN

Abstracts

EN
Novel enantiomerically pure tetramethylbithiophene
diphosphine oxides (tetraMe-BITIOPO)
featuring differently substituted aromatic rings at the
phosphorous atoms were synthesized, fully characterized
and isolated in enantiomerically pure form. The new
Lewis bases were tested as organocatalysts in two
different reactions involving trichlorosilyl compounds.
The introduction of electron donating substituents on the
aromatic rings connected to the phosphine oxide groups
positively affected the chemical and stereochemical
catalytic efficiency of these ligands. The new catalysts
were able to promote the allylation of aldehydes with
allyltrichlorosilane in up to 76% yield and up to 86%
enantiomeric excess (ee), and the direct aldol reaction to
afford β-hydroxy ketones in high diastereoselectivity (up
to 88:12 anti:syn ratio) and up to 72% ee.

Publisher

Year

Volume

2

Issue

1

Physical description

Dates

accepted
11 - 2 - 2015
online
15 - 6 - 2015
received
27 - 11 - 2014

Contributors

author
  • Dipartimento di Chimica, Universita’ degli Studi di
    Milano, via Golgi 19, 20133 Milano, Italy
  • Dipartimento di Chimica, Universita’ degli Studi di
    Milano, via Golgi 19, 20133 Milano, Italy
  • Dipartimento del Farmaco, Istituto Superiore di Sanità,
    viale Regina Elena 299, 00161 Roma, Italy
  • Dipartimento di Scienza ed Alta Tecnologia
    dell’Università dell’Insubria, via Valleggio, 11, 22100 Como, Italy

References

  • [1] Benaglia M., Rossi S., Chiral phosphine oxides in present-dayorganocatalysis, Org. Biomol. Chem., 2010, 8, 3824-3830.
  • [2] Rossi S., Benaglia M., Genoni A., Organic reactions mediatedby tetrachlorosilane, Tetrahedron, 2014, 70, 2065-2080.
  • [3] Simonini V., Benaglia M., Benincori T., A new class of chiralLewis basic metal-free catalysts for stereoselective allylationsof aldehydes, Adv. Synth. Catal., 2008, 350, 561-564;
  • [4] Nakajima M., Kotani S., Ishizuka T., Hashimoto S., Chiralphosphine oxide BINAPO as a catalyst for enantioselectiveallylation of aldehydes with allyltrichlorosilanes, TetrahedronLett., 2005, 46, 157-159.
  • [5] Chen J., Liu D., Fan D., Liu Y., Zhang W., Synthesis of axiallychiral C10-BridgePHOS oxides and their use as organocatalystsin enantioselective allylations of aldehydes, Tetrahedron, 2013,69, 8161-8168.
  • [6] Tokuoka E., Kotani S., Matsunaga H., Ishizuka T., HashimotoS., Nakajima M., Asymmetric ring opening of meso-epoxidescatalyzed by the chiral phosphine oxide BINAPO, Tetrahedron:Asymmetry, 2005, 16, 2391-2392.
  • [7] Kotani S., Furusho H., Sugiura M., Nakajima M., Facilesynthesis of chiral 1,2-chlorohydrins via the ring-openingof meso-epoxides catalyzed by chiral phosphine oxides,Tetrahedron, 2013, 69, 3075-3081.
  • [8] Nakanishi K., Kotani S., Sugiura M., Nakajima M., Firstasymmetric Abramov-type phosphonylation of aldehydeswith trialkyl phosphites catalyzed by chiral Lewis bases,Tetrahedron, 2008, 64, 6415-6419.
  • [9] Ohmaru Y., Sato N., Mizutani M., Kotani S., Sugiura M.,Nakajima M., Synthesis of aryl group-modified DIOP dioxides(Ar-DIOPOs) and their application as modular Lewis basecatalysts, Org. Biomol. Chem., 2012, 10, 4562-4570.
  • [10] Kashiwagi T. Kotani S., Sugiura M., Nakajima M., Synthesisof γ-amino alcohols from aldehydes, enamines, and trichlorosilaneusing Lewis base catalysts, Tetrahedron, 2011, 67,531-539.
  • [11] Sugiura M., Kumahara M., Nakajima M., Asymmetric synthesisof 4H-1,3-oxazines: enantioselective reductive cyclization ofN-acylated β-amino enones with trichlorosilane catalyzed bychiral Lewis bases, Chem Commun., 2009, 3585-3587.
  • [12] Kotani S., Hashimoto, S., Nakajima M., Chiral phosphine oxideBINAPO as a Lewis base catalyst for asymmetric allylation and aldol reaction of trichlorosilyl compounds, Tetrahedron, 2007,63, 3122-3132.
  • [13] Shimoda Y., Tando T., Kotani S., Sugiura M., Nakajima M.,Enantioselective aldol reaction of silyl ketene acetals promotedby a Lewis base-activated Lewis acid catalyst, Tetrahedron:Asymmetry, 2009, 20, 1369-1370.
  • [14] Kotani S., Aoki S., Sugiura M., Ogasawara, M., Nakajima M.,Phosphine Oxide-Catalyzed Enantioselective IntramolecularAldol Reaction via Regioselective Enolization of UnsymmetricalDiketones with Tetrachlorosilane, Org. Lett., 2014, 16,4802-4805.
  • [15] Genoni A., Benaglia M., Rossi S., Celentano G., EnantiomericallyPure Bithiophene Diphosphine Oxides as Catalysts forDirect Double Aldol Reactions, Chirality, 2013, 25, 643-647.
  • [16] Rossi S., Benaglia M., Genoni A., Benincori T., Celentano G.,Biheteroaromatic diphosphine oxides-catalyzed stereoselectivedirect aldol reactions, Tetrahedron, 2011, 67, 158-166.
  • [17] Kotani S., Sugiura M., Nakajima M., Enantioselective AldolReactions Catalyzed by Chiral Phosphine Oxides, Chem. Rec.2013, 13, 362-370.
  • [18] Aoki S., Kotani S., Sugiura M., Nakajima M., Trichlorosilyltriflate-mediated enantioselective directed cross-aldol reactionbetween ketones using a chiral phosphine oxide as an organocatalyst,Chem. Commun., 2012, 48, 5524-5526.
  • [19] Shimoda Y., Kotani S., Sugiura M., Nakajima M., EnantioselectiveDouble Aldol Reaction Catalyzed by Chiral PhosphineOxide, Chem Eur. J., 2011, 17, 7992-7995.
  • [20] Kotani S., Aoki S., Sugiura M., Nakajima M., Trichlorosilyltriflate for enantioselective direct-type aldol reactionwith chiral phosphine oxide, Tetrahedron Lett., 2011, 52,2834-2836.
  • [21] Kotani S., Shimoda Y., Sugiura M., Nakajima M., Novel enantioselectivedirect aldol-type reaction promoted by a chiralphosphine oxide as an organocatalyst, Tetrahedron Lett., 2009,50, 4602-4605.
  • [22] Shimoda, Y., Kubo T., Sugiura M., Kotani S., Nakajima M.,Stereoselective Synthesis of Multiple Stereocenters by Usinga Double Aldol Reaction, Angew. Chem. Int. Ed., 2013, 52,3461-3464.
  • [23] Zhang P., Han Z., Wang Z., Ding K., Spiro[4,4]-1,6-Nonadiene-Based Diphosphine Oxides in Lewis Base Catalyzed AsymmetricDouble-Aldol Reactions, Angew. Chem. Int. Ed., 2013, 52,11054-11058.
  • [24] Nakajima M., Kotani S., Sugiura M., Enantioselective DoubleAldol Reactions Involving the Sequential Activation of SiliconTetrachloride by Chiral Phosphine Oxides, Synlett, 2014, 25,631-640.
  • [25] Bonsignore M., Benaglia M., Cozzi F., Genoni A., Rossi S.,Raimondi L., Readily available (S) proline-derived organocatalystsfor the Lewis acid-mediated Lewis base-catalyzedstereoselective aldol reactions of activated thioesters,Tetrahedron, 2012, 68, 8251-8255.
  • [26] Rossi S., Benaglia M., Cozzi F., Genoni A., Benincori T., OrganocatalyticStereoselective Direct Aldol Reaction of TrifluoroethylThioesters, Adv. Synth. Catal., 2011, 353, 848-854.
  • [27] Osakama K., Sugiura M., Nakajima M., Kotani S., Enantioselectivereductive aldol reaction using tertiary amine as hydridedonor, Tetrahedron Lett., 2012, 53, 4199-4201.
  • [28] Sugiura M., Sato N., Sonoda Y., Kotani S., Nakajima M.,Diastereo- and Enantioselective Reductive Aldol Reaction withTrichlorosilane Using Chiral Lewis Bases as organocatalysts,Chem, Asian J., 2010, 5, 478-481.
  • [29] Kotani S., Ito M., Nozaki H., Sugiura M., Ogasawara M.,Nakajima M., Enantioselective Morita–Baylis–Hillman reactioncatalyzed by a chiral phosphine oxide, Tetrahedron Lett., 2013,54, 6430-6433.
  • [30] Denmark S.E., Beutner G.L., Lewis Base Catalysis in OrganicSynthesis, Angew. Chem. Int. Ed., 2008, 47, 1560-1638.
  • [31] Benincori T., Cesarotti E., Piccolo O., Sannicolò F.,2,2’,5,5’-Tetramethyl-4,4’-bis(diphenylphoshino)-3,3’-bithiophene: A New, Very Efficient, Easily Accessible, ChiralBiheteroaromatic Ligand for Homogeneous StereoselectiveCatalysis, J. Org. Chem., 2000, 65, 2043-2047.
  • [32] In this case, an inseparable mixture of mono- bis- andtriphosphoric chloride products were obtained.
  • [33] Mashima K., Kusano K.-h., Sato N., Matsumura Y.-i., NozakiK., Kumobayashi H., Sayo N., Hori Y., Ishizaki T., AkutagawaS., Takaya H., Cationic BINAP-Ru(II) Halide Complexes:Highly Efficient Catalysts for Stereoselective AsymmetricHydrogenation of alpha- and beta-Functionalized Ketones, J.Org. Chem., 1994, 59, 3064-3076.
  • [34] Yields were not optimized.
  • [35] For full characterization and spectroscopic data see: Rossi S.,Chiral Lewis bases activation of trichlorosilyl derivatives, PhDThesis, Università degli Studi di Milano, Milano, Italy, 2010.

Document Type

Publication order reference

Identifiers

YADDA identifier

bwmeta1.element.-psjd-doi-10_1515_asorg-2015-0002
JavaScript is turned off in your web browser. Turn it on to take full advantage of this site, then refresh the page.