90246-36-9Relevant academic research and scientific papers
Highly stereoselective kinetic resolution of α-allenic alcohols: An enzymatic approach
Li, Wenhua,Lin, Zuming,Chen, Long,Tian, Xuechao,Wang, Yan,Huang, Sha-Hua,Hong, Ran
supporting information, p. 603 - 606 (2016/01/20)
A highly efficient lipase AK-catalyzed direct kinetic resolution of a variety of α-allenic alcohols was developed. With the complementary to previous studies, the current reaction system is effective on a broad range of substituents (R1) at C(1), such as alkyl, aryl, alkenyl, and alkynyl groups. The Jones-Burgess empirical model was modified to interpret the reversed selectivity during the acetylation of secondary alcohol. The methyl group at C(2) of allenic alcohols implied a small structural adjustment in the catalytic triad of lipase AK, representing a potential direction for future site-directed mutagenesis.
[1,3]-Transfer of chirality during the nicholas reaction in γ-benzyloxy propargylic alcohols
Diaz, David D.,Ramirez, Miguel A.,Martin, Victor S.
, p. 2593 - 2606 (2008/02/07)
A highly regio- and stereoselective intramolecular [1.5]-hydrogentransfer process is described. Treatment of γ-benzyl-protccted Co 2(CO)6-α,γ-acetylenic diols with BF 3·OEt2 provides bis-homopropargylic alcohols. The reaction occurs within seconds, tolerates a wide range of functionalities, and provides good yields. When the ether group is located at a stereochemically defined carbon atom, the rearrangement occurs with high stereoselectivity, transferring the chirality of the carbinol center to the newly created stereocenter. The cleavage of the benzyloxy group is totally regioselective when additional benzyl ethers are present. The scope and limitations of this novel process in densely substituted substrates are evaluated, and possible competitive reactions and/or stereochemical influences are also described. A mechanism based on a highly ordered chair-like transition state substantiated by a theoretical study is also included.
A highly stereoselective synthesis of Z-disubstituted olefin by O-assisted Still-Wittig rearrangement
Fujii, Kazushige,Hara, Osamu,Fujita, Yoko,Sakagami, Youji
, p. 389 - 392 (2007/10/03)
In the Still-Wittig rearrangement, stannylated methyl (E)-allylic ethers having an aliphatic side chain (1a-c) exhibited the usual similar stereoselectivity, although the poor stereoselectivity was remarkably improved by the assistance of an alkoxy moiety on the alkenyl chain. A stannylated methyl (Z)-allylic ether bearing an alkoxy moiety on the alkenyl chain (1e) also showed a high E selectivity as previously reported.
