3844-94-8Relevant articles and documents
Thermal [3,3]-rearrangement of 1,1-disubstituted allyl carboxylates: Lone pair participation and the geminal bond participation
Naruse, Yuji,Deki, Aya,Yamada, Katsura
, p. 7035 - 7040 (2010)
The diastereoselectivity of the [3,3]-rearrangement of 1,1-disubsstituted allyl carboxylates was studied. In this heteroatom-containing system, the transition state has a boat-like transition structure (TS) because of the participation of the lone pairs and the secondary orbital interaction. Although the TS for the [1,3]-rearrangement has a far higher barrier, it does not proceed in the usual antarafacial manner due to the cyclic orbital interaction among two lone pairs of the carboxylate and the allylic lumo. In conjunction with the geminal bond participation, delocalization to the σ-bond at the Z-position shows a bonding character in the transition state of the [3,3]-rearrangement. Therefore, we predicted that a more electron-withdrawing σ-bond prefers the Z-position in the product. We designed the 1,1-disubstituted substrates with trimethylsilyl and pentyl groups, and found that the trimethylsilyl group prefers the Z-position despite its steric bulkiness. We confirmed our prediction by experimentation. This Z-selectivity was improved when a trimethylgermyl group was used.
Synthesis of cis-β-Amidevinyl Benziodoxolones from the Ethynyl Benziodoxolone-Chloroform Complex and Sulfonamides
Shimbo, Daisuke,Shibata, Atsushi,Yudasaka, Masaharu,Maruyama, Toshifumi,Tada, Norihiro,Uno, Bunji,Itoh, Akichika
supporting information, p. 9769 - 9773 (2019/11/28)
The synthesis of cis-β-amidevinyl benziodoxolones from the ethynyl benziodoxolone-chloroform complex and sulfonamides is reported. Evidence indicates that highly reactive unsubstituted ethynyl benziodoxolone undergoes Michael addition of sulfonamides, including sterically demanding acyclic amino acid derivatives. The synthesis of selectively deuterated cis-β-amidevinyl benziodoxolones and investigation of ethynyl-λ3-iodane reactivity are also described.
Influence of molecular length on the adsorption of linear trimethylsilylacetylene derivatives at the n-tetradecane/Au(111) interface: Chemisorption vs. Physisorption
Nion, Aymeric,Katsonis, Nathalie,Marchenko, Alexandre,Aubert, Corinne,Fichou, Denis
, p. 2261 - 2265 (2013/09/24)
Adsorption of two trimethylsilylacetylene (TMSA) derivatives bearing linear alkyl chains of different lengths has been studied at the n-tetradecane/Au(111) interface. The lying or standing orientation of TMSA compounds on the gold surface shows that adsorption is not only controlled by the chemical reactivity of the molecules but also by their size.
