| pubmed-article:18052247 | rdf:type | pubmed:Citation | lld:pubmed |
| pubmed-article:18052247 | lifeskim:mentions | umls-concept:C0679729 | lld:lifeskim |
| pubmed-article:18052247 | lifeskim:mentions | umls-concept:C0022634 | lld:lifeskim |
| pubmed-article:18052247 | lifeskim:mentions | umls-concept:C0007382 | lld:lifeskim |
| pubmed-article:18052247 | lifeskim:mentions | umls-concept:C0205372 | lld:lifeskim |
| pubmed-article:18052247 | lifeskim:mentions | umls-concept:C0441712 | lld:lifeskim |
| pubmed-article:18052247 | lifeskim:mentions | umls-concept:C1527178 | lld:lifeskim |
| pubmed-article:18052247 | pubmed:issue | 51 | lld:pubmed |
| pubmed-article:18052247 | pubmed:dateCreated | 2007-12-20 | lld:pubmed |
| pubmed-article:18052247 | pubmed:abstractText | The mechanism of the enantioselective cyanosilylation of ketones catalyzed by tertiary amino-thiourea derivatives was investigated using a combination of experimental and theoretical methods. The kinetic analysis is consistent with a cooperative mechanism in which both the thiourea and the tertiary amine of the catalyst are involved productively in the rate-limiting cyanide addition step. Density functional theory calculations were used to distinguish between mechanisms involving thiourea activation of ketone or of cyanide in the enantioselectivity-determining step. The strong correlation obtained between experimental and calculated ee's for a range of substrates and catalysts provides support for the most favorable calculated transition structures involving amine-bound HCN adding to thiourea-bound ketone. The calculations suggest that enantioselectivity arises from direct interactions between the ketone substrate and the amino-acid derived portion of the catalyst. On the basis of this insight, more enantioselective catalysts with broader substrate scope were prepared and evaluated experimentally. | lld:pubmed |
| pubmed-article:18052247 | pubmed:grant | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:18052247 | pubmed:language | eng | lld:pubmed |
| pubmed-article:18052247 | pubmed:journal | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:18052247 | pubmed:citationSubset | IM | lld:pubmed |
| pubmed-article:18052247 | pubmed:chemical | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:18052247 | pubmed:chemical | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:18052247 | pubmed:chemical | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:18052247 | pubmed:chemical | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:18052247 | pubmed:status | MEDLINE | lld:pubmed |
| pubmed-article:18052247 | pubmed:month | Dec | lld:pubmed |
| pubmed-article:18052247 | pubmed:issn | 1520-5126 | lld:pubmed |
| pubmed-article:18052247 | pubmed:author | pubmed-author:JacobsenEric... | lld:pubmed |
| pubmed-article:18052247 | pubmed:author | pubmed-author:ZuendStephan... | lld:pubmed |
| pubmed-article:18052247 | pubmed:issnType | Electronic | lld:pubmed |
| pubmed-article:18052247 | pubmed:day | 26 | lld:pubmed |
| pubmed-article:18052247 | pubmed:volume | 129 | lld:pubmed |
| pubmed-article:18052247 | pubmed:owner | NLM | lld:pubmed |
| pubmed-article:18052247 | pubmed:authorsComplete | Y | lld:pubmed |
| pubmed-article:18052247 | pubmed:pagination | 15872-83 | lld:pubmed |
| pubmed-article:18052247 | pubmed:meshHeading | pubmed-meshheading:18052247... | lld:pubmed |
| pubmed-article:18052247 | pubmed:meshHeading | pubmed-meshheading:18052247... | lld:pubmed |
| pubmed-article:18052247 | pubmed:meshHeading | pubmed-meshheading:18052247... | lld:pubmed |
| pubmed-article:18052247 | pubmed:meshHeading | pubmed-meshheading:18052247... | lld:pubmed |
| pubmed-article:18052247 | pubmed:meshHeading | pubmed-meshheading:18052247... | lld:pubmed |
| pubmed-article:18052247 | pubmed:meshHeading | pubmed-meshheading:18052247... | lld:pubmed |
| pubmed-article:18052247 | pubmed:meshHeading | pubmed-meshheading:18052247... | lld:pubmed |
| pubmed-article:18052247 | pubmed:meshHeading | pubmed-meshheading:18052247... | lld:pubmed |
| pubmed-article:18052247 | pubmed:year | 2007 | lld:pubmed |
| pubmed-article:18052247 | pubmed:articleTitle | Cooperative catalysis by tertiary amino-thioureas: mechanism and basis for enantioselectivity of ketone cyanosilylation. | lld:pubmed |
| pubmed-article:18052247 | pubmed:affiliation | Department of Chemistry & Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA. | lld:pubmed |
| pubmed-article:18052247 | pubmed:publicationType | Journal Article | lld:pubmed |
| pubmed-article:18052247 | pubmed:publicationType | Research Support, N.I.H., Extramural | lld:pubmed |
| http://linkedlifedata.com/r... | pubmed:referesTo | pubmed-article:18052247 | lld:pubmed |
| http://linkedlifedata.com/r... | pubmed:referesTo | pubmed-article:18052247 | lld:pubmed |
| http://linkedlifedata.com/r... | pubmed:referesTo | pubmed-article:18052247 | lld:pubmed |
