156540-94-2Relevant academic research and scientific papers
Iron-Catalyzed Regiodivergent Hydrostannation of Alkynes: Intermediacy of Fe(IV)-H versus Fe(II)-Vinylidene
Liu, Jianguo,Song, Heng,Wang, Tianlin,Jia, Jiong,Tong, Qing-Xiao,Tung, Chen-Ho,Wang, Wenguang
supporting information, p. 409 - 419 (2021/01/12)
We report an iron system, Cp*Fe(1,2-R2PC6H4X), which controls the Markovnikov and anti-Markovnikov hydrostannation of alkynes by tuning the ionic metal-heteroatom bonds (Fe-X) reactivity. The sequential addition of nBu3SnH to the iron-amido catalyst (1, X = HN-, R = Ph) affords a distannyl Fe(IV)-H species responsible for syn-addition of the Sn-H bond across the CC bond to produce branched α-vinylstannanes. Activation of the C(sp)-H bond of alkynes by an iron-aryloxide catalyst (2, X = O-, R = Cy) affords an iron(II) vinylidene intermediate, allowing for gem-addition of the Sn-H to the terminal-carbon producing β-vinylstannanes. These catalytic reactions exhibit excellent regioselectivity and broad functional group compatibility and enable the large-scale synthesis of diverse vinylstannanes. Many new reactions have been established based on such a synthetic Fe-X platform to demonstrate that the initial step of the catalysis is conveniently controlled by the activation of either the tin hydride or the alkyne substrate.
Copper-catalyzed α-selective hydrostannylation of alkynes for the synthesis of branched alkenylstannanes
Yoshida,Shinke,Kawano,Takaki
supporting information, p. 10616 - 10619 (2015/06/30)
A variety of branched alkenylstannanes can directly be synthesized with excellent α-selectivity by the copper-catalyzed hydrostannylation using a distannane or a silylstannane, irrespective of the electronic and steric characteristics of terminal alkynes employed. Synthetic utility of the resulting branched alkenylstannane has been demonstrated by the total synthesis of bexarotene.
Total synthesis of (-)-ophiodilactone A and (-)-ophiodilactone B
Matsubara, Takaaki,Takahashi, Keisuke,Ishihara, Jun,Hatakeyama, Susumi
, p. 757 - 760 (2014/01/23)
The first asymmetric total synthesis of (-)-ophiodilactone A and (-)-ophiodilactone B, isolated from the ophiuroid (Ophiocoma scolopendrina), is reported. The key features of the synthesis include the highly stereocontrolled construction of the structurally congested γ-lactone/δ-lactone skeleton through an asymmetric epoxidation, diastereoselective iodolactonization, and intramolecular epoxide-opening with a carboxylic acid, and biomimetic radical cyclization of ophiodilactone A to ophiodilactone B. Bioinspired synthesis: The first total synthesis of the title compounds has been accomplished in a highly stereocontrolled manner. Key features of the synthesis include an asymmetric epoxidation, a diastereoselective iodolactonization, an intramolecular epoxide opening with a carboxylic acid, and a biomimetic radical cyclization of ophiodilactone A to ophiodilactone B. Copyright
Lewis acid-catalyzed hydrometalation and carbometalation of unactivated alkynes
Asao, Naoki,Yamamoto, Yoshinori
, p. 1071 - 1087 (2007/10/03)
Hydrosilylation, hydrostannation, carbosilylation, and carbostannation of unactivated alkynes with organosilanes, or organostannanes proceed effectively in the presence of catalytic amounts of Lewis acids to produce the corresponding vinylsilyl or vinylst
Hydrostannation of C-C multiple bonds with Bu3SnH prepared in situ from Bu3SnCl and Et3SiH in the presence of Lewis acid catalysts
Gevorgyan, Vladimir,Liu, Jian-Xiu,Yamamoto, Yoshinori
, p. 37 - 38 (2007/10/03)
A number of alkynes 5, allene 11 and alkene 13 smoothly underwent hydrostannation with tributyltin hydride 1, prepared in situ from tributylchlorostannane 6 and triethylsilane 7 in the presence of catalytic amounts of Lewis acids.
