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George M. Whitesides

Publications and source records attributed to George M. Whitesides.

7 recordsLinked to original sources
PubMed2001

Correlating Electron Transport and Molecular Structure in Organic Thin Films This work was supported by the Office of Naval Research, the Defense Advanced Research Project Agency, and the National Science Foundation ECS-97294053. R.E.H. thanks the National Institutes of Health for a postdoctoral fellowship, and R.H. thanks the Deutsche Forschungsgemeinschaft and the BASF fellowship program for financial support. We thank Andreas Terfort for the synthesis of aromatic thiols. Collaboration between Caracas and Evanston is supported by NSF Conicit.

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PubMed1996

Synthesis of C-5 Analogs of N-Acetylneuraminic Acid via Indium-Mediated Allylation of N-Substituted 2-Amino-2-deoxymannoses.

This paper presents a short synthesis of new analogs of N-acetylneuraminic acid (Neu5Ac) varied structurally at C-5. The synthetic strategy includes indium-mediated coupling reactions between ethyl 2-(bromomethyl)acrylate and N-derivatized mannosamines, and the ozonolysis of the resulting enoates. The main advantage of this indium-mediated allylation for the synthesis of neuraminic acids comes from the efficient, stereoselective C-C bond formation, which affords predominantly the correct diastereomer having a threo relationship between the newly generated hydroxyl group and the C-2 amide group of mannosamine. By this approach, Neu5Boc (4a), Neu5Gly (4b), Neu5(6-NHCbz)hexanoyl (4c), and Neu5(1-naphthyl)acetyl (4d) were prepared in three steps (overall approximately 50%). In addition, several N-substituted neuraminic acids were synthesized by N-acylation of the amino functionality of neuraminic acid (5b), which was obtained by deprotecting the N-Boc group of Neu5Boc (4a). These analogs include Neu5BrAc (6a), Neu5acryloyl (6b), Neu5benzoyl (6c) and Neu5benzoyl-4-benzoyl (6d). The N-acylation method is especially suited for synthesis of neuraminic acids bearing substituents that can not tolerate ozonolysis or that are unstable (photo)chemically. Finally, we illustrate the utility of synthetic neuraminic acids by converting 4c to a derivative of 2-deoxy-2,3-didehydroneuraminic acid (8c), a precursor to inhibitors of neuraminidases.

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PubMed1996

Synthesis and Evaluation of Thioether-Based Tris-Melamines as Components of Self-Assembled Aggregates Based on the CA.M Lattice.

Two new tris-melamine derivatives, triazine-thio-M(3) (5) (C(3)N(3)-2,4,6-[SCH(2)C(6)H(4)-3-N(CH(2)C(6)H(4)-4-C(CH(3))(3))COC(6)N(3)-2-NHC(3)N(3)(NH(2))(NHCH(2)CH(2)C(CH(3))(3))-5-Br](3)) and benzene-thio-M(3) (6) (C(6)H(3)-1,3,5-[SCH(2)C(6)H(4)-3-N(CH(2)C(6)H(4)-4-C(CH(3))(3))COC(6)H(3)-2-NHC(3)N(3)(NH(2))(NHCH(2)CH(2)C(CH(3))(3))-5-Br](3)), were synthesized by reactions of 2,4,6-trithiocyanuric acid and 1,3,5-trimercaptobenzene with a bromobenzyl melamine derivative 19 (BrCH(2)C(6)H(4)-3-N(CH(2)C(6)H(4)-4-C(CH(3))(3))COC(6)H(3)-2-NHC(3)N(3)(NH(2))(NHCH(2)CH(2)C(CH(3))(3))-5-Br). These two compounds formed stable and structurally well-defined 1 + 3 supramolecular aggregates with neohexyl isocyanurate (R'CA) (9) as shown by NMR spectroscopy and gel permeation chromatography. (1)H NMR competition experiments indicated that the stability of triazine-thio-M(3).(R'CA)(3) (1) was similar to that of benzene-thio-M(3).(R'CA)(3) (2). The order of stabilities of tris-melamine-based 1 + 3 complexes was hubM(3).(R'CA)(3) (3) > triazine-thio-M(3).(R'CA)(3) (1) approximately benzene-thio-M(3).(R'CA)(3) (2) > flexM(3).(R'CA)(3) (4). Computational simulations were also carried out on triazine-thio-M(3).(R'CA)(3) and hubM(3).(R'CA)(3) fully solvated in CHCl(3). Values of DP (the deviation from planarity of the cyanuric acid and melamine rosette) obtained from these simulations correlated correctly with the observed stabilities and suggested a structural reason why triazine-thio-M(3).(R'CA)(3) was less stable than hubM(3).(R'CA)(3).

Journal Article↗
PubMed1996

Stereoselective alpha-Sialylation with Sialyl Xanthate and Phenylsulfenyl Triflate as a Promotor.

Reaction alpha- and beta-xanthates 2 and 3 of sialic acid with glycosyl acceptors 5-8 in the presence phenylsulfenyl triflate (PST) as a promotor in a 2:1 mixture of CH(3)CN/CH(2)Cl(2) at low temperature affords alpha-sialosides in good yield and stereoselectivity. PST is prepared in situ by reacting benzenesulfenyl chloride with silver triflate. Less reactive acceptors 5 and 6 give a higher alpha/beta ratio than more reactive allylic alcohol 7 and primary alcohol 8; alpha-stereoselectivity is increased in a dilute solution. A possible mechanism of the reaction that involves intermediate alpha- and beta-nitrilium cations 16 and 17 is discussed.

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