3240-29-7Relevant academic research and scientific papers
Nickelocene-Lithium Aluminum Hydride: A Versatile Desulfurization Reagent
Chan, Man-Chor,Cheng, Kwok-Man,Ho, Kim Man,Ng, Chi Tat,Yam, Tsz Man,et al.
, p. 4466 - 4471 (1988)
A new homogeneous organonickel reagent prepared from nickelocene and LiAlH4 has been shown to be effective for the reduction of the carbon-sulfur bonds of thiols, thioethers, sulfoxides, and sulfones to the corresponding carbon-hydrogen bonds.Functional groups such as isolated double bonds, esters, and carbonyls as well as halides remain intact under the reaction conditions.Preliminary studies on the nature of the reagent and the mechanism for the reaction have been carried out by employing deuterium labeling experiments and spectroscopic methods.Metal hydridic species may play an important role in these reactions.The reagent can also be used to reduce the carbon-carbon double bond of conjugate enones and catalyze hydrogenation of carbon-carbon multiple bonds.A comparison of the reaction behavior of this newly developed reagent with that of Raney nickel is discussed.
A new radical-ionic allylation sequence
Briggs, Michael E.,Zard, Samir Z.
, p. 334 - 336 (2005)
Fluoride induced elimination of β-xanthylsilanes, formed by the radical addition of xanthates to allylsilanes, leads to the formation of diversely substituted allyl derivatives.
An allylstannane reagent on non-cross-linked polystyrene support
Enholm, Eric J.,Gallagher, Maria E.,Moran, Kelley M.,Lombardi, Jennifer S.,Schulte II, James P.
, p. 689 - 691 (1999)
Formula presented A new allylstannane reagent on non-cross-linked polystyrene was developed for the first time. This support differs markedly from standard cross-linked polymers because it is completely soluble in organic solvents; moreover, the reactions
Catalytic Diverse Radical-Mediated 1,2-Cyanofunctionalization of Unactivated Alkenes via Synergistic Remote Cyano Migration and Protected Strategies
Wang, Na,Li, Lei,Li, Zhong-Liang,Yang, Ning-Yuan,Guo, Zhen,Zhang, Hong-Xia,Liu, Xin-Yuan
, p. 6026 - 6029 (2016)
A catalytic radical protocol for 1,2-cyanofunctionalization of unactivated alkenes involving remote cyano migration triggered by addition of diverse carbon- and heteroatom-centered radicals to alkenes has been developed. This powerful strategy provides a
ETHOXYACETYLENE: A USEFUL BUILDING BLOCK FOR THE ORGANOCOPPER(I) MEDIATED SYNTHESIS OF 1,4-DIKETONES
Wijkens, P.,Vermeer, P.
, p. 247 - 256 (1986)
Ethoxyacetylene (I) has been converted by organocopper(I) species into (E)-2-ethoxy-1-alkenylcopper(I) compounds (II).The adducts II have been to shown be useful intermediates for preparation of 1,4-diketones (VI).Two routes to VI were used: (i) sequential treatment of II with allyl bromide, 3.0 N HCl, and PdCl2/CuCl in DMF/H2O, and (ii) sequential treatment of II with 2,3-dibromopropane and Hg(OAc)2.A dienone was formed from the first procedure when after the reaction of II with allyl bromide the product was treated first with the PdCl2/CuCl.
Preparation of Primary and Secondary Dialkylmagnesiums by a Radical I/Mg-Exchange Reaction Using sBu2Mg in Toluene
Knochel, Paul,Lutter, Ferdinand H.,Sunagatullina, Alisa S.
, (2022/02/16)
The treatment of primary or secondary alkyl iodides with sBu2Mg in toluene (25–40 °C, 2–4 h) provided dialkylmagnesiums that underwent various reactions with aldehydes, ketones, acid chlorides or allylic bromides. 3-Substituted secondary cyclohexyl iodides led to all-cis-3-cyclohexylmagnesium reagents under these exchange conditions in a highly stereoconvergent manner. Enantiomerically enriched 3-silyloxy-substituted secondary alkyl iodides gave after an exchange reaction with sBu2Mg stereodefined dialkylmagnesiums that after quenching with various electrophiles furnished various 1,3-stereodefined products including homo-aldol products (99 % dr and 98 % ee). Mechanistic studies confirmed a radical pathway for these new iodine/magnesium-exchange reactions.
Lewis Acid-Catalyzed Halonium Generation for Morpholine Synthesis and Claisen Rearrangement
Ariyarathna, Jeewani P.,Alom, Nur-E,Roberts, Leo P.,Kaur, Navdeep,Wu, Fan,Li, Wei
, p. 2947 - 2958 (2022/02/23)
We disclose here practical strategies toward the synthesis of morpholines and Claisen rearrangement products based on the divergent reactivity of a common halonium intermediate. These reactions employ widely available alkenes in a Lewis acid-catalyzed halo-etherification process that can then transform them into the desired products with exceptional regioselectivity for both activated and unactivated olefins. Our mechanistic probe reveals an interesting regiochemical kinetic resolution process.
Nickel-catalyzed remote hydrosilylation of unconjugated enones with bulky triphenylsilane
Chen, Xue,Wang, Zhen,Zhou, Jinyong,Liu, Yunkui,Jin, Hongwei,Zhou, Bingwei
supporting information, p. 8021 - 8024 (2021/10/04)
Herein we describe a nickel-catalyzed remote hydrosilylation of unconjugated enones with bulky triphenylsilane. A range ofZ-silyl enol ethers are obtained as major isomers due to the process of nickel triggered alkene isomerization. Notably, some specific
Selective Synthesis of Z-Silyl Enol Ethers via Ni-Catalyzed Remote Functionalization of Ketones
Guven, Sinem,Kundu, Gourab,Rissanen, Kari,Schoenebeck, Franziska,Ward, Jas S.,We?els, Andrea
supporting information, p. 8375 - 8380 (2021/06/27)
We report a remote functionalization strategy, which allows the Z-selective synthesis of silyl enol ethers of (hetero)aromatic and aliphatic ketones via Ni-catalyzed chain walking from a distant olefin site. The positional selectivity is controlled by the directionality of the chain walk and is independent of thermodynamic preferences of the resulting silyl enol ether. Our mechanistic data indicate that a Ni(I) dimer is formed under these conditions, which serves as a catalyst resting state and, upon reaction with an alkyl bromide, is converted to [Ni(II)-H] as an active chain-walking/functionalization catalyst, ultimately generating a stabilized η3-bound Ni(II) enolate as the key selectivity-controlling intermediate.
Diastereoselective and Stereodivergent Synthesis of 2-Cinnamylpyrrolines Enabled by Photoredox-Catalyzed Iminoalkenylation of Alkenes
Shen, Xu,Huang, Congcong,Yuan, Xiang-Ai,Yu, Shouyun
, p. 9672 - 9679 (2021/03/16)
A photoredox-catalyzed iminoalkenylation of γ-alkenyl O-acyl oximes has been developed. Readily available alkenylboronic acids serve as alkenylation reagents, leading to densely functionalized pyrrolines. Both (E)- and (Z)-cinnamylpyrrolines are accessible depending on the reaction solvent. In dichloromethane, (E)-cinnamylpyrrolines are produced through a photoredox-mediated single-electron-transfer process. In tetrahydrofuran, (Z)-cinnamylpyrrolines are generated by photocatalytic contra-thermodynamic E-to-Z isomerization of (E)-cinnamylpyrrolines though an energy-transfer pathway. Two stereocenters are established with complete diastereoselectivity and only one diastereomer is isolated.
