781-33-9Relevant academic research and scientific papers
Method for hydrocarbylation synthesis of trisubstituted and tetrasubstituted olefins from non-terminal olefins
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Paragraph 0054-0063; 0079-0081, (2021/02/06)
The invention discloses a method for hydrocarbylation synthesis of trisubstituted and tetrasubstituted olefins from non-terminal olefins, wherein the method comprises the steps: carrying out hydrocarbylation reaction on the non-terminal olefins and sulfoxide in the presence of ferric salt and hydrogen peroxide, carrying out one-pot reaction on disubstituted non-terminal olefins to generate the trisubstituted olefins, and carrying out one-pot reaction on the trisubstituted non-terminal olefins to generate the tetrasubstituted olefins. In the method, sulfoxide is simultaneously used as a hydrocarbylation reagent and a solvent of olefins, and one more hydrocarbyl substituent is added to a reaction product compared with a double-bond carbon atom of a reactant, so that an olefin carbon chain isincreased; the reaction conditions are mild, the selectivity is good, the yield is high, and industrial production is facilitated.
Synthesis of Allylboronates via Zweifel-type Deprotonative Olefination
Xu, Nuo,Xu, Jianeng,Zhu, Qing,Liu, Chao
, p. 2403 - 2407 (2020/12/30)
A method for the synthesis of allylboronates via Zweifel-type deprotonative olefination was demonstrated. Tetrasubstituted vinylboronates were used as the substrates. NCS (N-chlorosuccinimide) was used as a bifunctional additive, electrophile and base. This method exhibited a different elimination strategy in Zweifel type transformation to afford allylboronates. The homo-alcohols and alkenes were stereoselective synthesized from the obtained allylboronates, demonstrating the synthetic value of this methodology. (Figure presented.).
Method for synthesizing alkyl olefin through coupling of double-bond carbon-hydrogen bond and saturated carbon-hydrogen bond
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Paragraph 0070-0073; 0096, (2021/02/10)
The invention discloses a method for synthesizing alkyl olefin through coupling of a double-bond carbon-hydrogen bond and a saturated carbon-hydrogen bond. According to to the method, one-pot reactionis implemented on olefin and sulfoxide in the presence of ferric salt and hydrogen peroxide to generate alkyl olefin; in the method, sulfoxide is simultaneously used as a hydrocarbylation reagent anda solvent of olefin, and a reaction product is alkyl olefin from sulfoxide alkyl coupled with olefin carbon atoms, so that an olefin carbon chain is increased; the reaction conditions are mild, the selectivity is good, the yield is high, and industrial production is facilitated.
Spiro[1,2]oxaphosphetanes of nonstabilized and semistabilized phosphorus ylide derivatives: Synthesis and kinetic and computational study of their thermolysis
López, Jesús García,Sansores Peraza, Pablo M.,Iglesias, María José,Roces, Laura,García-Granda, Santiago,Ortiz, Fernando López
, p. 14570 - 14591 (2020/11/20)
A series of tri- and tetrasubstituted spiro-oxaphosphetanes stabilized by ortho-benzamide (oBA) and N-methyl ortho-benzamide (MoBA) ligands have been synthesized by the reaction of Cα,Cortho-dilithiated phosphazenes with aldehydes and ketones. They include enantiopure products and the first example of an isolated oxaphosphetane having a phenyl substituent at C3 of the ring. Kinetic studies of their thermal decomposition showed that the process takes place irreversibly through a polar transition state (ρ = -0.22) under the influence of electronic, [1,2], [1,3] steric, and solvent effects, with C3/P-[1,2] interactions as the largest contribution to ΔG of olefination. Inversion of the phosphorus configuration through stereomutation has been observed in a number of cases. DFT calculations showed that oBA derivatives olefinated through the isolated (N, O)(Ph, C6H4, C) oxaphosphetanes (Channel A), whereas MoBA compounds decomposed faster via the isomer (C6H4, O)(C, N, Ph) formed by P-stereomutation involving a MB2 permutational mechanism (Channel B). The energy barrier of P-isomerization is lower than that of olefination. Fragmentation takes place in a concerted asynchronous reaction. The thermal stability of oxaphosphetanes is determined by strong C3/P-[1,2] interactions destabilizing the transition state of olefination. The effect of charge distribution and C3/C4-[1,2] and C4/P-[1,3] steric and solvent interactions on ΔG was also evaluated.
Conversion of Carbonyl Compounds to Olefins via Enolate Intermediate
Cao, Zhi-Chao,Xu, Pei-Lin,Luo, Qin-Yu,Li, Xiao-Lei,Yu, Da-Gang,Fang, Huayi,Shi, Zhang-Jie
supporting information, p. 781 - 785 (2019/06/24)
A general and efficient protocol to synthesize substituted olefins from carbonyl compounds via nickel catalyzed C—O activation of enolates was developed. Besides ketones, aldehydes were also suitable substrates for the presented catalytic system to produce di- or tri- substituted olefins. It is worth noting that this approach exhibited good tolerance to highly reactive tertiary alcohols, which could not survive in other reported routes for converting carbonyl compounds to olefins. This method also showed good regio- and stereo-selectivity for olefin products. Preliminary mechanistic studies indicated that the reaction was accomplished through nickel catalyzed C—O activation of enolates, thus offering helpful contribution to current enol chemistry.
Catalytic Functionalization of Styrenyl Epoxides via 2-Nickela(II)oxetanes
Desnoyer, Addison N.,Geng, Jialing,Drover, Marcus W.,Patrick, Brian O.,Love, Jennifer A.
supporting information, p. 11509 - 11512 (2017/08/30)
Low-valent nickel is shown to preferentially isomerize mono- or disubstituted epoxides into their corresponding aldehydes. Experiments with tetrasubstituted epoxides demonstrate that these reactions proceed via reactive 2-nickelaoxetane intermediates, and
Nickel-Catalyzed Direct Synthesis of Aryl Olefins from Ketones and Organoboron Reagents under Neutral Conditions
Lei, Chuanhu,Yip, Yong Jie,Zhou, Jianrong Steve
supporting information, p. 6086 - 6089 (2017/05/08)
Nickel-catalyzed addition of arylboron reagents to ketones results in aryl olefins directly. The neutral condition allows acidic protons of alcohols, phenols, and malonates to be present, and fragile structures are also tolerated.
Diradical reaction mechanisms in [3 + 2]-cycloadditions of hetaryl thioketones with alkyl- or trimethylsilyl-substituted diazomethanes
Mlostoń, Grzegorz,Pipiak, Paulina,Heimgartner, Heinz
, p. 715 - 724 (2016/07/06)
Reactions of dihetaryl and aryl/hetaryl thioketones with 2-diazopropane, diazoethane, and (trimethylsilyl)diazomethane were studied at variable temperature. The experiments showed that reactions with 2-diazopropane carried out at -75°C occur mainly via th
Metal-free oxidative cross-coupling of diazirines with arylboronic acids
Wu, Guojiao,Zhao, Xia,Ji, Wenzhi,Zhang, Yan,Wang, Jianbo
, p. 1961 - 1963 (2016/02/05)
We report herein a metal-free cross-coupling of diazirines with arylboronic acids under oxidative conditions. The reaction affords a series of substituted olefins. It is proposed that the interaction between the nitrogen on diazirine with arylboronic acid plays a key role in this transformation.
Pt-Catalyzed Rearrangement of Oxaspirohexanes to 3-Methylenetetrahydrofurans: Scope and Mechanism
Malapit, Christian A.,Chitale, Sampada M.,Thakur, Meena S.,Taboada, Rosa,Howell, Amy R.
, p. 5196 - 5209 (2015/05/27)
A novel Pt-catalyzed rearrangement of oxaspirohexanes to 3-methylenetetrahydrofurans is reported. Mechanistic studies by 13C-labeling experiments confirm oxidative addition of Pt(II) regioselectively to the least substituted carbon-carbon bond
