Asymmetric Lewis acid organocatalysis of the Diels–Alder reaction by a silylated C-H acid
Silylium ion equivalents have shown promise as Lewis acid catalysts for a range of important C–C bond-forming reactions. Here we describe chiral C–H acids that upon in situ silylation, generate silylium-carbanion pairs, which are extremely active Lewis acid catalysts for enantioselective Diels–Alder...
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| Veröffentlicht in: | Science (American Association for the Advancement of Science) 2016-02, Vol.351 (6276), p.949-952 |
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| container_title | Science (American Association for the Advancement of Science) |
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| creator | Gatzenmeier, Tim van Gemmeren, Manuel Xie, Youwei Höfler, Denis Leutzsch, Markus List, Benjamin |
| description | Silylium ion equivalents have shown promise as Lewis acid catalysts for a range of important C–C bond-forming reactions. Here we describe chiral C–H acids that upon in situ silylation, generate silylium-carbanion pairs, which are extremely active Lewis acid catalysts for enantioselective Diels–Alder reactions of cinnamates with cyclopentadiene. Enantiomeric ratios of up to 97:3 and diastereomeric ratios of more than 20:1 are observed across a diverse set of substitution patterns with 1 mole percent (mol %) of C–H acid catalyst and 10 mol % of a silylating reagent. The results show promise for broad applications of such C–H acid–derived silylium ion equivalents in asymmetric Lewis acid catalysis. |
| doi_str_mv | 10.1126/science.aae0010 |
| format | Article |
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Here we describe chiral C–H acids that upon in situ silylation, generate silylium-carbanion pairs, which are extremely active Lewis acid catalysts for enantioselective Diels–Alder reactions of cinnamates with cyclopentadiene. Enantiomeric ratios of up to 97:3 and diastereomeric ratios of more than 20:1 are observed across a diverse set of substitution patterns with 1 mole percent (mol %) of C–H acid catalyst and 10 mol % of a silylating reagent. The results show promise for broad applications of such C–H acid–derived silylium ion equivalents in asymmetric Lewis acid catalysis.</abstract><cop>United States</cop><pub>American Association for the Advancement of Science</pub><pmid>26917765</pmid><doi>10.1126/science.aae0010</doi><tpages>4</tpages></addata></record> |
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| subjects | Acids Catalysis Catalysts Chemical reactions |
| title | Asymmetric Lewis acid organocatalysis of the Diels–Alder reaction by a silylated C-H acid |
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