研究领域
Applications of Organometallic Complexes in catalysis/biological applications and in development of functional materials
Research Interest
Development of Transition Metal based Catalytic Systems:
We are currently investigating the use of Ru, Pd and Ir metallacycles and related systems for their potential as catalysts in various organic synthetic scenarios. We are also actively pursuing the development of catalytic protocols for the asymmetric generation of new chiral phosphines from non chiral substrates, especially those incorporating the ferrocenyl moiety and having planar, axial and central chirality elements and their subsequent application in asymmetric synthesis.
Development of High Oxidation State Metal Complexes as Therapeutic agents:
The activation of transition metal based prodrugs by reduction is a plausible pathway that has been attracting increasing attention because their complexes possess a biologically accessible MIV/MIII/MII redox potential. Various ligands have the potential to stabilize high oxidation states of metals like Ruthenium and Iridium. This makes the development of such complexes interesting for the preparation of bio-reductive pro-drugs which are activated by reduction in the acidic extracellular environment of the hypoxic tumor tissue. We are currently working on drug candidates which not only involve high oxidation state metal centres but also incorporate ligands which when liberated could act as iron chelators.
Our other interests include use of organometallic systems in the synthesis of functional materials and the development of high chiral density structural motifs.
近期论文
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S.A.Pullarkat* and P.H.Leung*, Chiral Metal Complex Promoted Asymmetric Hydrophosphinations, In Topics in Organometallic Chemistry: Hydrofunctionalization, Tanaka M Ed., Springer, New York, 2013, 43:145-166.
J.H.Gan, C.Xu, L.Curless and S.A.Pullarkat*, Asymmetric Construction of a Ferrocenyl Phosphapalladacycle from Achiral Enones and a Demonstration of Its Catalytic Potential, Organometallics, 2014, DOI: 10.1021/om5007215.
X.Yang, J.H.Gan, Y.Li, S.A.Pullarkat* and P.H.Leung*, Palladium Catalyzed asymmetric Hydrophosphination of alpha,beta- and alpha,beta,gamma,delta-unsaturated Malonate Esters- Efficient Control of Reactivity, Stereo- and Regio-Slectivity, Dalton Trans., 2014, accepted
X. Yang, Y. Li and S.A. Pullarkat*, A One-Pot Diastereoselective Self Assembly of C-Stereogenic Supramolecular Copper (II) Diphosphine Clusters., Inorg. Chem., 2014, DOI: 10.1021/ic501233w.
J.Wong, J.H. Gan, H.J. Chen and S.A. Pullarkat*, Evaluation of Palladacycles as a Non-Rhodium Alternative for the Asymmetric Conjugate 1,4-Addition of Aryl Boronic Acids to alpha,beta-Unsaturated Enones, Adv. Synth. Catal., 2014, accepted.
K.Chen, J. Yang, C.Jeremy, W.Jonathan and S.A.Pullarkat*, Copper (II) triflate Catalyzed Allylic Arylation of Allylic Alcohols-Direct and Selective Access to C-Allylanilines, ChemCatChem., 2013, 5, 3882-3888.
D.Krishnan, M.Wu, M.Chiang,, Y. Li P.H.Leung* and S.A.Pullarkat*. N-Heterocyclic Carbene C,S Palladium(II) pi-Allyl Complexes: Synthesis, Characterization and Catalytic Application in Allylic Amination Reaction, Organometallics, 2013, 32(8), 2389-2397.
K.H.Ng, Y.Li, W.X.Tan, M.Chiang and S.A.Pullarkat*, Rigid Chiral Pyridine-N-Heterocyclic Carbene Based Pallaacycles with an Unexpected Pd-N Bond Cleavage, Chirality, 2013, 25, 149-159.
K.Chen and S.A.Pullarkat*, A Tandem Heck- aza-Michael Addition Protocol for the One-Pot Synthesis of Isoindolines from Unprotected Amines, Org. Biomol. Chem., 2012, 10, 6600-6606.
C.Xu, V.Kumar and S.A.Pullarkat*, Domino Cyclization-Alkylation Protocol for the Synthesis of 2,3-functionalized Indoles from 0-alkynylanilines and Allylic Alcohols, Org. Biomol. Chem., 2012, 10, 3875-3881 (Highlighted in ChemInform).
C.Xu, G.J.H.Kennard, F.Hennersdorf, Sumod A. Pullarkat*, and P.H.Leung*, Palladacycle catalyzed asymmetric synthesis of malonate derived monodentate phosphines, Organometallics, 2012, 31(8), 3022-3026.
C.K.Chen, Y.Li, S.A.Pullarkat* and P.H.Leung*, Palladacycle Catalyzed Tandem Allylic Amination/Allylation Protocol for the One-Pot Synthesis of 2-Allylailines from Allylic Alcohols, Adv. Synth. Catal., 2012, 354, 83-87 (Highlighted in ChemInform)
C.Xu, L.W.Chuan, Y.Li and S.A. Pullarkat*, Ruthenacycles as efficient catalysts for the beta-alkylation of secondary alcohols with primary alcohols, Tet. Lett., 2012, 53, 1450-1455 (Highlighted in Cheminform).
C.Xu, Y.Li, L.Y.Goh and S.A.Pullarkat*, An Ir-thioether-dithiolate Catalyst for low catalyst loading Beta-alkylation and selective imine formation via N-Alkylations Reactions, Organometallics, 2011, 30, 6499-6502.
Y.Huang, R.J.Chew, Y.Li, S.A.Pullarkat* and P.H.Leung*, Direct Synthesis of Chiral Tertiary Diphosphines via Pd(II) catalyzed asymmetric hydrophosphination, Org. Lett., 2011, 13, 5862-5865.
C.Xu, L.Y.Goh* and S.A.Pullarkat*, New Thioether-dithiolate Complexes of Cp*Ir and some reactivity features , J. Organomet. Chem., 2011, 26, 4207-4214.
C.Xu, S.A.Pullarkat* and L.Y.Goh*, Bis(allyl)ruthenium(IV)-initiated S-S and C-S Bond Cleavages in Tetraalkylthiuram Sulfides: Formation and X-ray Crystal structures of Dithiocarbamato Complexes, Aus. J. Chem., 2009, 62(11), 1537-1543.
Y.X.Jia, B.B.Li, Y.Li, S.A. Pullarkat, H.Hirao and P.H.Leung, Stereoelectronic and Catalytic Properties of Chiral Cyclometallated Phospha-palladium and -platinum Complexes, Organometallics, 2014, doi:10.1021/om500662q.
R.J.Chew, Y. Lu, Y.X. Jia, B. Li, H.Y.W. Ester, R.Goh, Y. Li, Y. Huang, S.A. Pullarkat and P.H.Leung, Palladacycle Catalyzed Asymmetric P-H Addition of Diarylphosphines to N-Enoyl Phthalimides, Chem. Eur. J., 2014, doi:10.1002/chem.201403885.
R.J. Chew, K.Y. Teo, Y. Huang, B.Li, Y.Li, S.A. Pullarkat and P.H. Leung, Enantioselective Phospha-Michael Addition of Diarylphosphines to unsaturated alpha-ketoesters and amides, Chem. Comm., 2014, 50, 8768-8770.