Influence of the Organocatalyst in the Aldol/Mannich-Type Product Selectivities in C-C Bond Forming Reactions

被引：25

作者：

de Maria, Pablo Dominguez ^{[1
]}

Bracco, Paula ^{[1
]}

Castelhano, Luiz Fernando ^{[1
]}

Bargeman, Gerrald ^{[1
]}

机构：

[1] AkzoNobel BV, Proc & Prod Technol Dept CPT, NL-6800 SB Arnhem, Netherlands

来源：

ACS CATALYSIS | 2011年 / 1卷 / 02期

关键词：

proline; pyrrolidine; oxazolidinone; aldol; mannich; organocatalysis; ASYMMETRIC ALDOL REACTIONS; TRIFLUOROACETALDEHYDE ETHYL HEMIACETAL; AMINO-ACIDS; CONDENSATION-REACTIONS; ALDEHYDE-ALDEHYDE; L-PROLINE; KETONES; CHEMISTRY; OXAZOLIDINONES; DIARYLPROLINOL;

D O I：

10.1021/cs100088m

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Several organocatalysts were tested in the cross condensation of isobutyraldehyde and acetone. Formation of aldol-type and Mannich-type ("aldol condensation") products was assessed, and Aldol/Mannich proportion studied under several reaction conditions and at different conversions. Organocatalysts able to form Seebach's oxazolidinones, proline and prolinol, led to high Aldol/Mannich relationships (60-10, depending on organocatalyst, reaction conditions, and conversions), whereas organocatalysts unable to form such oxazolidinones (pyrrolidine, O-methylprolinol and proline 'butyl ester) yielded much lower Aldol/Mannich relationships in all conditions and conversions studied (<2.8). These results suggest that Seebach's oxazolidinones might act as "controllers" of the reaction, thus partly avoiding the formation of the Mannich-type adducts, by removing activated forms of aldehyde from the catalytic cycle.

引用

页码：70 / 75

页数：6

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