16212-07-0Relevant articles and documents
Palladium-triethylborane-triggered direct and regioselective conversion of allylic alcohols to allyl phenyl sulfones?
Chandrasekhar, Srivari,Jagadeshwar, Vannada,Saritha, Birudaraju,Narsihmulu, Cheryala
, p. 6506 - 6507 (2005)
A combination of Pd(OAc)2 (5 mol %), PPh3 (10 mol %), and Et3B (200 mol %) promotes the formation of allyl phenyl sulfones from the allylic alcohols directly with excellent yields under mild conditions. The activation of an alcohol group is not necessary which is achieved in situ. The conjugated dienols also were equally effective for the said transformation.
Isomerisation of Vinyl Sulfones for the Stereoselective Synthesis of Vinyl Azides
Collins, Niall,Connon, Robert,Evans, Paul,Sánchez-Sanz, Goar
supporting information, p. 6228 - 6235 (2020/10/02)
Reported is the construction, and facile base-mediated conversation of ten differently substituted 3-azido E-vinyl sulfones (γ-azido-α,β-unsaturated sulfones) into their isomeric vinyl azide counterparts. The requisite 3-azido E-vinyl sulfones were prepared from 3-bromo E-vinyl sulfones, which in turn were accessed from allyl sulfones via a bromination-elimination sequence. In relation to this a one-pot azidation-isomerisation sequence was developed which enabled the direct formation of the vinyl azides from the corresponding 3-bromo E-vinyl sulfones. Similarly, a convenient one-pot Horner–Wadsworth–Emmons olefination-isomerisation approach was utilised in order to prepare some of the allylic sulfones used in this study. The vinyl azide forming process typically proceeded with high levels of Z-selectivity, although this was dependent on the vinyl sulfone substitution pattern. Thus, with either no substituent or a methyl group in the γ- or β-position, relative to the sulfone, good, to high levels of Z-selectivity (Z/E = 85:15 to ≥ 95:5) were obtained. However, incorporation of an α-sulfonyl methyl substituent led to an E-selective process (Z/E = 20:80). A non-bonding interaction between the azido group and the α-sulfonyl vinylic proton is proposed, which acts as a conformational control mechanism to help guide the stereochemical outcome.
Reciprocal-Activation Strategy for Allylic Sulfination with Unactivated Allylic Alcohols
Xie, Peizhong,Sun, Zuolian,Li, Shuangshuang,Cai, Xinying,Qiu, Ju,Fu, Weishan,Gao, Cuiqing,Wu, Shisheng,Yang, Xiaobo,Loh, Teck-Peng,Loh, Teck-Peng
supporting information, p. 4893 - 4897 (2020/06/24)
A reciprocal-activation strategy for allylic sulfination with unactivated allylic alcohols was developed. In this reaction, the hydrogen bond interaction between allylic alcohols and sulfinic acids allowed for reciprocal activation, which enabled a dehydrative cross-coupling process to occur under mild reaction conditions. This reaction worked in an environmentally friendly manner, yielding water as the only byproduct. A variety of allylic sulfones could be obtained in good to excellent yields with wide functional group tolerance. In gram scale reactions, allylic sulfones could be conveniently isolated in high yield by filtration.
Vinylethylene Carbonates as α,β-Unsaturated Aldehyde Surrogates for Regioselective [3 + 3] Cycloaddition
Xu, Yi,Chen, Lu,Yang, Yu-Wen,Zhang, Zhiqiang,Yang, Weibo
, p. 6674 - 6678 (2019/09/03)
Herein, we report a novel stepwise addition-controlled ring size method, to access tetrahydropyrimidines through an operationally simple [3 + 3] cycloaddition of vinylethylene carbonates with triazinanes. Interestingly, we could also use this method for a [3 + 3] oxidative cycloaddition, which allows the facile synthesis of polysubstituted terphenyls under mild conditions. Mechanistic studies suggest that vinylethylene carbonates could generate α,β-unsaturated aldehydes as 3-carbon synthons for cycloaddition via a combination process of Pd-catalyzed decarboxylation and β-H elimination.
Sulfinate-Engaged Nucleophilic Addition Induced Allylic Alkylation of Allenoates
Lin, Ling-Zhi,Che, Yuan-Yuan,Bai, Peng-Bo,Feng, Chao
, p. 7424 - 7429 (2019/10/02)
A strategically novel Pd-catalyzed nucleophilic addition induced allylic alkylation reaction (NAAA) of allenoates has been successfully accomplished. By judiciously integrating ZnCl2-promoted Michael addition with Pd-catalyzed allylic alkylation, allenoates readily undergo allyl-sunfonylation at the internal double bond, thus providing a straightforward avenue for the rapid assembly of a host of structurally diversified α-allyl-β-sufonylbut-3-enoate derivatives. The success of this transformation profits from a delicate control of the reaction kinetic of each elementary step, thanks to the synergistic interaction of Pd/Zn bimetallic system, thus suppressing either direct allylic sulfonylation or premature quenching of therein in situ generated ester enolate intermediate. Furthermore, by expanding the scope of workable Michael acceptor beyond those previously required doubly activated ones, such as methylenemalononitrile, the present work substantially enriches the repertoire of NAAA reactions.
Allyl sulfone compound and preparation method and application thereof
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, (2020/01/12)
The invention discloses an allyl sulfone compound and a preparation method and application thereof. The preparation method comprises the following steps of sequentially adding allyl alcohol, sulfinicacid, palladium tetrakis(triphenylphosphine) and calcium bis(trifluoromethylsulfonyl)imide into a reaction solvent in an inert gas atmosphere, and carrying out a reaction under stirring for 12-48 h atthe temperature of 30 DEG C, wherein the equivalent ratio of allyl alcohol, sulfinic acid, palladiumtetrakis(triphenylphosphine) and calcium bis(trifluoromethylsulfonyl)imide is 1: (1.5-2): (1-3%): (5-10%); and removing the reaction solvent in the reaction liquid, and then performingpurifying to obtain the allyl sulfone compound. The preparation method disclosed by the invention is high in economy and wide in applicable substrate range; in addition, the obtained allyl sulfone compound has potential pharmaceutical activity and biological activity and is an important skeleton widely existing inbiologically and pharmaceutically active molecules.
Regioselective Single-Electron Tsuji-Trost Reaction of Allylic Alcohols: A Photoredox/Nickel Dual Catalytic Approach
Wang, Zheng-Jun,Zheng, Shuai,Romero, Eugénie,Matsui, Jennifer K.,Molander, Gary A.
supporting information, p. 6543 - 6547 (2019/08/26)
A radical-mediated functionalization of allyl alcohol derived partners with a variety of alkyl 1,4-dihydropyridines via photoredox/nickel dual catalysis is described. This transformation transpires with high linear and E-selectivity, avoiding the requirement of harsh conditions (e.g., strong base, elevated temperature). Additionally, using aryl sulfinate salts as radical precursors, allyl sulfones can also be obtained. Kinetic isotope effect experiments implicated oxidative addition of the nickel catalyst to the allylic electrophile as the turnover-limiting step, supporting previous computational studies.
Bis(phenylsulfonyl)methane mediated synthesis of olefins: Via a halogen elimination and double bond migration
Hu, Yanwei,Jiang, Jing,Hu, Ying,Cai, Xin,Wang, Liudi,Chen, Shaohua,Zhang, Shilei,Zhang, Yinan
, p. 2619 - 2622 (2018/04/27)
An effective dehydrochlorination of bis(phenylsulfonyl)alkane to prepare alkene building blocks is developed. The elimination together with double bond migration results in a variety of β,γ-unsaturated bis(phenylsulfonyl)olefins in good yields with only E geometry. The following chemical diversification represents an easy and straightforward access to a series of alkene building blocks.
Alkenylation of C(sp3)?H Bonds by Zincation/Copper-Catalyzed Cross-Coupling with Iodonium Salts
Liu, Chuan,Wang, Qiu
supporting information, p. 4727 - 4731 (2018/03/21)
α-Vinylation of phosphonates, phosphine oxides, sulfones, sulfonamides, and sulfoxides has been achieved by selective C?H zincation and copper-catalyzed C(sp3)?C(sp2) cross-coupling reaction using vinylphenyliodonium salts. The vinylation transformation proceeds in high efficiency and stereospecificity under mild reaction conditions. This zincative cross-coupling reaction represents a general alkenylation strategy, which is also applicable for α-alkenylation of esters, amides, and nitriles in the synthesis of β,γ-unsaturated carbonyl compounds.
Oxidative Allylic Esterification of Alkenes by Cooperative Selenium-Catalysis Using Air as the Sole Oxidant
Ortgies, Stefan,Depken, Christian,Breder, Alexander
supporting information, p. 2856 - 2859 (2016/07/06)
A new metal-free catalysis protocol for the oxidative coupling of nonactivated alkenes with simple carboxylic acids has been established. This method is predicated on the cooperative interaction of a diselane and a photoredox catalyst, which allows for the use of ambient air or pure O2 as the terminal oxidant. Under the title conditions, a range of both functionalized and nonfunctionalized alkenes can be readily converted into the corresponding allylic ester products with good yields (up to 89%) and excellent regioselectivity as well as good functional group tolerance.
