- Substitution of allylic acetates with sodium para-toluenesulfinate in aqueous media using allylpalladium chloride dimer and a water-soluble ligand as the catalytic system; electrospray ionisation mass spectrometry analysis
-
The allylic substitution of allylic acetates by sodium para- toluenesulfinate in aqueous media was catalyzed by [(η3-allyl) PdCl]2 associated with [(HOCH2CH2NHCOCH 2)2NCH2]2. High yields could be obtained but the recycling of the catalytic system proved to be weakly effective. ESI-MS analysis has led to the suggestion of a possible catalytic cycle involving a PdIV intermediate. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.
- Chevrin, Carole,Le Bras, Jean,Roglans, Anna,Harakat, Dominique,Muzart, Jacques
-
-
Read Online
- Vinylethylene Carbonates as α,β-Unsaturated Aldehyde Surrogates for Regioselective [3 + 3] Cycloaddition
-
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.
- Xu, Yi,Chen, Lu,Yang, Yu-Wen,Zhang, Zhiqiang,Yang, Weibo
-
p. 6674 - 6678
(2019/09/03)
-
- Regioselective Single-Electron Tsuji-Trost Reaction of Allylic Alcohols: A Photoredox/Nickel Dual Catalytic Approach
-
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.
- Wang, Zheng-Jun,Zheng, Shuai,Romero, Eugénie,Matsui, Jennifer K.,Molander, Gary A.
-
supporting information
p. 6543 - 6547
(2019/08/26)
-
- Sodium Arenesulfinates-Involved Sulfinate Synthesis Revisited: Improved Synthesis and Revised Reaction Mechanism
-
Reaction of alcohols with sodium arenesulfinates could afford either sulfones or sulfinates, and O-attack of sulfinate anions onto the in situ generated carbocation intermediates from alcohols was the previous proposed reaction mechanism in many syntheses of sulfinates. This concept, which is often used consciously or unconsciously, was revised herein by using isotopic labeling experiments and development of an improved sulfinate synthesis. The improved sulfinate synthetic protocol possesses many advantages such as a high sulfinate/sulfone selectivity, a broad substrate scope, metal-free, and mild reaction conditions. The revised reaction mechanism necessitates revision of many previous proposed reaction mechanisms in literatures.
- Ji, Yuan-Zhao,Li, Hui-Jing,Zhang, Jin-Yu,Wu, Yan-Chao
-
p. 1846 - 1855
(2019/02/14)
-
- Green and Scalable Palladium-on-Carbon-Catalyzed Tsuji–Trost Coupling Reaction Using an Efficient and Continuous Flow System
-
The first continuous flow Tsuji–Trost coupling reaction between allylic compounds and various nucleophiles has been successfully achieved within only around 40 s during a single pass through a cartridge filled with palladium on carbon (Pd/C). Two methods have been designed by using the H-cube ThalesNano technology that enable the efficient production of added-value compounds on the gram scale with high productivity. Under the optimized conditions, the cartridge catalyst can be used for 60 min of continuous processing without a decrease in reactivity. A large range of substrates and nucleophiles have successfully been submitted to the standard methods, giving good-to-excellent yields and productivity.
- Cazorla, Clément,Billamboz, Muriel,Bricout, Hervé,Monflier, Eric,Len, Christophe
-
p. 1078 - 1085
(2017/02/23)
-
- Micellar catalysis using a photochromic surfactant: Application to the pd-catalyzed tsuji-trost reaction in water
-
The first example of a Pd-catalyzed Tsuji-Trost reaction, applied in a photochromic micellar media under conventional heating and microwave irradiation, is reported. The surfactant activity and recycling ability were investigated and compared with those of a few commercially available surfactants. The synthetic photochromic surfactant proved to be efficient, recyclable, and versatile for Pdcatalyzed coupling reactions.
- Billamboz, Muriel,Mangin, Floriane,Drillaud, Nicolas,Chevrin-Villette, Carole,Banaszak-Leonard, Estelle,Len, Christophe
-
p. 493 - 500
(2014/04/03)
-
- Coupling reaction of magnesium alkylidene carbenoids with α-sulfonylallyllithiums: An efficient route to multi-substituted vinylallenes
-
A variety of vinylallenes were successfully synthesized from 1-chlorovinyl p-tolyl sulfoxides and allyl or vinyl sulfones. Allyl and vinyl sulfones served as α-sulfonylallyllithium sources were prepared from carbonyl compounds in three or four steps in good overall yields. The coupling reaction of α-sulfonylallyllithiums with magnesium alkylidene carbenoids, which were generated from 1-chlorovinyl p-tolyl sulfoxides and isopropylmagnesium chloride, afforded multi-substituted vinylallenes in up to 88% yield. Georg Thieme Verlag KG Stuttgart · New York.
- Kimura, Tsutomu,Kobayashi, Gen,Ishigaki, Masashi,Inumaru, Mio,Sakurada, Jo,Satoh, Tsuyoshi
-
p. 3623 - 3632
(2013/02/23)
-
- Direct substitution of primary allylic amines with sulfinate salts
-
The NH2 group in primary allylic amines was substituted directly by sulfinate salts with excellent regio- and stereoselectivities. In the presence of 0.1 mol % [Pd(allyl)Cl]2, 0.4 mol % 1,4- bis(diphenylphosphino)butane (dppb), and excess boric acid, a range of α-unbranched primary allylic amines were smoothly substituted with sodium sulfinates in an α-selective fashion to give structurally diverse allylic sulfones in good to excellent yields with exclusive E selectivity. Replacing dppb with 1,1′-bi-2-naphthol (BINOL) allowed unsymmetric α-chiral primary allylic amines to be transformed into the corresponding allylic sulfones in good to excellent yields with excellent retention of ee. Importantly, the reaction complements known asymmetric methods in substrate scope via its unique ability to provide α-chiral allylic sulfones with high optical purity starting from unsymmetric allylic electrophiles.
- Wu, Xue-Song,Chen, Yan,Li, Man-Bo,Zhou, Meng-Guang,Tian, Shi-Kai
-
supporting information
p. 14694 - 14697
(2012/11/07)
-
- Synthesis of sulfones by iron-catalyzed decomposition of sulfonylhydrazones
-
The Fe-catalyzed decomposition of sulfonylhydrazones gives rise to sulfones. The reaction is quite general and allows the preparation of sulfones from a variety of aryl, alkyl, and α,β-unsaturated aldehydes and ketones. Crossover experiments reveal that the reaction is an intermolecular process, which may proceed by nucleophilic attack of the sulfinate anion on an iron carbene complex. Carbonyl compounds can be easily transformed into sulfones by Fe-catalyzed decomposition of the corresponding sulfonylhydrazones. The process most likely proceeds through an iron carbene complex and opens the door for the design of othernovel Fe-catalyzed reductive couplings. Copyright
- Barluenga, Jose,Tomas-Gamasa, Maria,Aznar, Fernando,Valdes, Carlos
-
experimental part
p. 1520 - 1526
(2011/04/25)
-
- An unexpected reaction of arenesulfonyl cyanides with allylic alcohols: Preparation of trisubstituted allyl sulfones
-
(Chemical Equation Presented) An efficient and practical protocol for the highly selective preparation of substituted allyl sulfones has been developed. Arenesulfonyl cyanides, Baylis-Hillman adducts, and simple allylic alcohols give an unforeseen outcome
- Reddy, Leleti Rajender,Hu, Bin,Prashad, Mahavir,Prasad, Kapa
-
experimental part
p. 172 - 174
(2009/04/10)
-
- Practical Pd/C-mediated allylic substitution in water
-
Pd/C-mediated allylic substitution in water is described as an interesting alternative to classical homogeneous conditions. The reaction applied to allylic acetates showed a wide range of compatibility with various nitrogen, sulfur, oxygen, and carbon nucleophiles. Notably, the method features inexpensive reagents and a nontoxic solvent. Moreover, measurement of the palladium content in water by ICP-MS shows low palladium contamination (4 ppm) of the solvent, rendering this method safer for the environment compared to homogeneous conditions. The first asymmetric example of Pd/C-mediated allylic substitution is also disclosed.
- Felpin, Francois-Xavier,Landais, Yannick
-
p. 6441 - 6446
(2007/10/03)
-
- Synthesis of sulfones from arenesulfonyl chlorides and alkyl halides using the Sm/HgCl2 bimetallic system
-
A simple and convenient procedure for the synthesis of sulfones from arenesulfonyl chlorides and alkyl halides using the Sm/HgCl2 bimetallic system in tetrahydrofuran is presented.
- Zhang, Jiming,Zhang, Yongmin
-
p. 516 - 517
(2007/10/03)
-
- Palladium catalyzed hydrosulfination of allenes with tosylhydrazine leading to allylsulfones
-
The palladium catalyzed reaction of allenes 1 with tosylhydrazine in the presence of 1 equiv AcOH and 10 mol% dppf gave the corresponding allylsufones 2 in moderate to good yields.
- Kamijo, Shin,Al-Masum, Mohammad,Yamamoto, Yoshinori
-
p. 691 - 694
(2007/10/03)
-
- Indium-mediated Coupling Reaction of Sulfonyl Chlorides with Alkyl Bromides in Water. A Facile Synthesis of Sulfones
-
Indium-mediated coupling of alkyl bromides with aromatic sulfonyl chlorides gives the corresponding sulfones in aqueous media with moderate to good yields.
- Wang, Lei,Zhang, Yongmin
-
p. 588 - 589
(2007/10/03)
-
- "Syn-Effect" in the Conversion of (E)-Vinylic Sulfones to the Corresponding Allylic Sulfones
-
It was found that (E)-vinylic sulfones preferentially afford (Z)-allylic sulfones as kinetically-controlled products by treatment with a base under mild conditions, while (Z)-vinylic sulfones give (E)-allylic sulfones.Such stereochemical relationship was
- Hirata, Takaki,Sasada, Yoshihiro,Ohtani, Takashi,Asada, Takahiro,Kinoshita, Hideki,et al.
-
-
- Palladium(0)-catalyzed substitution of allylic substrates in a two-phase aqueous-organic medium
-
Palladium(0)-catalyzed substitution of allylic substrates are shown to occur in a two-phase aqueousorganic medium using the sulfonated triphenylphosphine P(C6H4-m-SO3Na)3 or (tppts) as the ligand, allowing the easy recovery and recycling of the catalyst.
- Safi, Mohamed,Sinou, Denis
-
p. 2025 - 2028
(2007/10/02)
-
- Stereochemistry of the Conversion of γ-substituted (E)-Vinylsulfones to the Corresponding Allylsulfones. Determination of the Relative Degree of "Syn-Effect"
-
The relative degree of "syn-effect" for the γ-substituted vinylsulfones in their conversion to the corresponding allylsulfones with 1,8-diazabicycloundec-7-ene (DBU) was determined by observing E/Z ratios of the resulting allylsulfones as follows:
- Inomata, Katsuhiko,Hirata, Takaki,Suhara, Hiroshi,Kinoshita, Hideki,Kotake, Hiroshi,Senda, Hitoshi
-
p. 2009 - 2012
(2007/10/02)
-
- SINGLE-STEP PREPARATION OF ALLYLIC SULFIDES HAVING 1-PHENYLTETRAZOLE-5-THIO GROUP FROM ALLYLIC ALCOHOLS USING S,S'-BIS(1-PHENYL-1H-TETRAZOL-5-YL) DITHIOCARBONATE AND REACTIONS INVOLVING THE ALLYLIC SULFIDES
-
The reaction of allylic alcohols and S,S'-bis(1-phenyl-1H-tetrazol-5-yl) dithiocarbonate (1) gave allylic sulfides having 1-phenyltetrazole-5-thio group in a single step.Furthermore, these allylic sulfides could be applied to carbon-carbon bond and carbon-sulfur bond formations by using Grignard reagents or carbanions in the presence of catalytic amount of copper(I) bromide or palladium (0), respectively.
- Takeda, Kazuyoshi,Tsuboyama, Kanoko,Torii, Katsumi,Murata, Maki,Ogura, Haruo
-
p. 4105 - 4108
(2007/10/02)
-
- Studies on Chiral Organo-Sulfur Compounds. II. Stereochemistry of Thermal Chiral Allyl Sulfinate-Sulfone Rearrangements
-
A highly efficient and general synthetic route to optically active sulfinates by the stereospecific boron trifluoride etherate-catalyzed esterification of sulfinamides was developed.Dramatic solvent effects were observed in the thermal transformation of allyl sulfinate derivatives to sulfones.Heating of chiral trans- and cis-allyl sulfinates, (S)-(-)-3a,c,e and (S)-(-)-3b,d,f, in N,N-dimethylformamide at 90-120 deg C provided chiral sulfones (S)-(+)- and (R)-(-)-5,6,7 in good yields, respectively, with exceedingly high stereospecificity. Keywords - asymmetric transfer; stereospecificity; chiral allyl sulfinate; chiral allyl sulfone; boron trifluoride etherate; thermolysis
- Hiroi, Kunio,Kitayama, Ryuichi,Sato, Shuko
-
p. 2628 - 2638
(2007/10/02)
-
- REGIO- AND STEREOCONTROLLED SYNTHESIS OF ALLYLIC p-TOLYL SULFONES CATALYZED BY PALLADIUM (0) COMPLEX
-
The reaction of allyl esters with sodium p-tolylsulfinate in tetrahydrofuran and methanol catalyzed by Pd(PPh3)4 gave the regio- and stereocontrolled allylic p-tolyl sulfones in good yields at room or lower temperature.
- Inomata, Katsuhiko,Yamamoto, Taku,Kotake, Hiroshi
-
p. 1357 - 1360
(2007/10/02)
-