摘要
The frustrated Lewis pair (FLP) Mes 2PCH 2CH 2B(C 6F 5) 2 (1) reacts with an enolizable conjugated ynone by 1,4-addition involving enolate tautomerization to give an eight-membered zwitterionic heterocycle. The conjugated endione PhCO-CH=CH-COPh reacts with the intermolecular FLP tBu 3P/B(C 6F 5) 3 by a simple 1,4-addition to an enone subunit. The same substrate undergoes a more complex reaction with the FLP 1 that involves internal acetal formation to give a heterobicyclic zwitterionic product. FLP 1 reacts with dimethyl maleate by selective overall addition to the C=C double bond to give a six-membered heterocycle. It adds analogously to the triple bond of an acetylenic ester to give a similarly structured six-membered heterocycle. The intermolecular FLP P(o-tolyl) 3/B(C 6F 5) 3 reacts analogously with acetylenic ester by trans-addition to the carbon-carbon triple bond. An excess of the intermolecular FLP tBu 3P/B(C 6F 5) 3, which contains a more nucleophilic phosphane, reacts differently with acetylenic ester examples, namely by O-C(alkyl) bond cleavage to give the {R-CO 2[B(C 6F 5) 3] 2 -}[alkyl-PtBu 3 +] salts. Simple aryl or alkyl esters react analogously by using the borane-stabilized carboxylates as good leaving groups. All essential products were characterized by X-ray diffraction.
源语言 | 英语 |
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页(从-至) | 1347-1356 |
页数 | 10 |
期刊 | Chemistry - An Asian Journal |
卷 | 7 |
期 | 6 |
DOI | |
出版状态 | 已出版 - 6月 2012 |
已对外发布 | 是 |