- Base-Mediated Radical Borylation of Alkyl Sulfones
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A practical and direct method was developed for the production of versatile alkyl boronate esters via transition metal-free borylation of primary and secondary alkyl sulfones. The key to the success of the strategy is the use of bis(neopentyl glycolato) diboron (B2neop2), with a stoichiometric amount of base as a promoter. The practicality and industrial potential of this protocol are highlighted by its wide functional group tolerance, the late-stage modification of complex compounds, no need for further transesterification, and operational simplicity. Radical clock, radical trap experiments, and EPR studies were conducted which show that the borylation process involves radical intermediates.
- Huang, Mingming,Hu, Jiefeng,Krummenacher, Ivo,Friedrich, Alexandra,Braunschweig, Holger,Westcott, Stephen A.,Radius, Udo,Marder, Todd B.
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supporting information
(2021/12/02)
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- Cu-mediated: vs. Cu-free selective borylation of aryl alkyl sulfones
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A Cu-catalysed borylation of aryl alkyl sulfones was developed for the high yield synthesis of versatile arylboronic esters using a readily prepared NHC-Cu catalyst. In addition, the selective cleavage of either alkyl(C)-sulfonyl or aryl(C)-sulfonyl bonds
- Hu, Jiefeng,Huang, Mingming,Marder, Todd B.,Radius, Udo,Tang, Man,Westcott, Stephen A.
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supporting information
p. 395 - 398
(2022/01/19)
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- One-pot synthesis of sulfones via Ni(II)-catalyzed sulfonylation of boronic acids, Na2S2O5 and benzylic ammonium salts
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A one-pot nickel-catalyzed synthesis of (hetero)aryl alkyl sulfones from readily available boronic acids, sodium metabisulfite and benzylic ammonium salts as electrophiles is described. This general and efficient synthetic process is of broad scope, occurs in two steps, and delivers structural diverse sulfones, and the intermediate sulfinate is isolated. The transformation exhibits application of benzylic ammonium salts as novel electrophiles for direct insertion of SO2 as a novel area to be investigated.
- Zhu, Haibo,Liu, Yishuai,Zhang, Yingying,Yang, Liu,Meng, Jia,Li, Qian,Gong, Bozhen,Xie, Zongbo,Le, Zhang-Gao
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- Cu2O-catalyzed C–S coupling of quaternary ammonium salts and sodium alkane-/arene-sulfinates
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A new protocol for the synthesis of (enantioenriched) benzylic sulfones via the Cu2O-catalyzed C–S bond cross coupling of alkane-/arene-sulfinates and (enantioenriched) benzylic quaternary ammonium salts has been developed. The product benzylic sulfones were obtained in good to high yields (75–96%). Chiral arylmethyl sulfones with high enantiomeric excess (90–94% ee) were also synthesized in the presence of Cu2O and 1,1′-bis-(diphenylphosphino)ferrocene (dppf).
- Chen, Hongyi,Huang, Youming,Zeng, Qingle,Zheng, Wenting
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- Manganese-Catalyzed Acceptorless Dehydrogenative Coupling of Alcohols with Sulfones: A Tool to Access Highly Substituted Vinyl Sulfones
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The development of first-row-transition-metal catalysts that can match with the reactivities of the noble metals is considered to be challenging yet very much a desirable goal in homogeneous catalysis. It has become even more fascinating to develop processes where these metals show a unique reactivity and selectivity than their higher congeners. Herein, we report on the catalytic activity of a pincer complex of the abundant earth metal manganese for an unprecedented acceptorless dehydrogenative coupling of alkyl sulfones with alcohols. Thus, highly functionalized vinyl sulfones were obtained in moderate to good yields. Both benzylic and aliphatic alcohols could be utilized, and several functional groups including bromides and iodides are tolerated under the reaction conditions. The reaction is environmentally benign, producing dihydrogen and water as byproducts. Preliminary mechanistic experiments involving kinetic, deuterium-labeling, and NMR experiments were performed.
- Barman, Milan K.,Maji, Biplab,Waiba, Satyadeep
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p. 973 - 982
(2021/08/24)
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- Modular synthesis of triarylmethanes through palladium-catalyzed sequential arylation of methyl phenyl sulfone
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Triarylmethanes, which are valuable structures in materials, sensing and pharmaceuticals, have been synthesized starting from methyl phenyl sulfone as an inexpensive and readily available template. The three aryl groups were installed through two sequential palladium-catalyzed C-H arylation reactions, followed by an arylative desulfonation. This method provides a new synthetic approach to multisubstituted triarylmethanes using readily available haloarenes and aryl boronic acids, and is also valuable for the preparation of unexplored triarylmethane-based materials and pharmaceuticals. Unsymmetric triarylmethanes have been synthesized starting from methyl phenyl sulfone as an inexpensive and readily available template. The three aryl groups were installed through two sequential palladium-catalyzed C-H arylation reactions, followed by an arylative desulfonation. Copyright
- Nambo, Masakazu,Crudden, Cathleen M.
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supporting information
p. 742 - 746
(2014/01/23)
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- Palladium-catalyzed direct α-arylation of methyl sulfones with aryl bromides
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A direct and efficient approach for palladium-catalyzed arylation of aryl and alkyl methyl sulfones with aryl bromides has been developed. The catalytic system affords arylated sulfones in good to excellent yields (73-90%).
- Zheng, Bing,Jia, Tiezheng,Walsh, Patrick J.
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supporting information
p. 1690 - 1693
(2013/06/26)
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- Highly atom-economic, catalyst- and solvent-free oxidation of sulfides into sulfones using 30% aqueous H2O2
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Highly atom-efficient oxidation of sulfides into sulfones under solvent- and catalyst-free reaction conditions using a 30% aqueous solution of H 2O2 at 75 °C is reported. A structurally diverse set of phenyl alkyl-, phenyl benzyl-, benzyl alkyl-, dialkyl-, heteroaryl alkyl- and cyclic sulfides were transformed into sulfones regardless of the aggregate state and electronic nature of the substituents. In spite of the heterogeneous reaction mixtures throughout the work, no difficulties with stirring and reaction progress were noted. In numerous cases, only 10 mol% excess of H 2O2 was used, thus contributing considerably to the high atom economy of the process. Some solid substrates required a variable excess of hydrogen peroxide; however, the reactions were performed strictly without organic solvents. The transformation was demonstrated to be amenable for scale-up with both liquid and solid sulfides. In addition, isolation and purification of the crude products can be simply done with only filtration and crystallization.
- Jereb, Marjan
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supporting information
p. 3047 - 3052,6
(2020/09/16)
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- Palladium-catalyzed Negishi α-arylation of alkylsulfones
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A general, mild catalytic system for α-monoarylation of various alkyl sulfones is described that utilizes palladium-catalyzed Negishi cross-coupling approach.
- Zhou, Gang,Ting, Pauline C.,Aslanian, Robert G.
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experimental part
p. 939 - 941
(2010/05/18)
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- Catalyst-free alkylation of sulfinic acids with sulfonamides via sp 3 C-N bond cleavage at room temperature
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An unprecedented catalyst-free alkylation of sulfinic acids with sulfonamides has been developed via sp3 C-N bond cleavage at room temperature. In the absence of external catalysts and additives, a wide variety of N-benzylic and N-allylic sulfonamides couple with sulfinic acids to give structurally diversified sulfones in moderate to excellent yields. Furthermore, the reaction of N-(2-acyl)allylic sulfonamides with sulfinic acids provides a convenient access to trisubstituted allyl sulfones with exclusive Z selectivity.
- Liu, Cong-Rong,Li, Man-Bo,Cheng, Dao-Juan,Yang, Cui-Feng,Tian, Shi-Kai
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supporting information; scheme or table
p. 2543 - 2545
(2009/10/10)
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- An expeditious entry to benzylic and allylic sulfones through byproduct-catalyzed reaction of alcohols with sulfinyl chlorides
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(Chemical Equation Presented) In the absence of external catalysts and additives, a broad range of benzylic and allylic alcohols react with various sulfinyl chlorides to afford structurally diversified benzylic and allylic sulfones in moderate to excellen
- Li, Hai-Hua,Dong, De-Jun,Jin, Yin-Huan,Tian, Shi-Kai
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supporting information; experimental part
p. 9501 - 9504
(2010/03/04)
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- Double elimination protocol for the synthesis of arylene ethynylenes containing heteroaromatic rings
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The double elimination reaction of β-substituted sulfones offers a versatile strategy for synthesis of arylene ethynylene kits containing heteroaromatic rings. A sequence of aldol reaction between α-sulfonyl carbanion and aldehyde, trapping the resulting aldolate to give β-substituted sulfone, and double elimination of this intermediate can be integrated in one pot. This protocol allows thiophene, pyridine, and ferrocene units to be accommodated in phenylene ethynylene arrays.
- Orita, Akihiro,Ye, Fangguo,Babu, Govindarajulu,Ikemoto, Tomohiro,Otera, Junzo
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p. 716 - 727
(2007/10/03)
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- Transformation of carbonates into sulfones at the benzylic position via palladium-catalyzed benzylic substitution
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(Chemical Equation Presented) The nucleophilic substitution of benzylic carbonates with sodium arenesulfinates was catalyzed by the palladium complex generated in situ from [Pd(η3-C3H5)Cl] 2 and DPEphos [bis(2-diphenylphosphinophenyl)ether]. The catalytic reaction proceeded in DMSO at 80°C and gave a variety of benzylic sulfones in high yields.
- Kuwano, Ryoichi,Kondo, Yutaka,Shirahama, Tsuyoshi
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p. 2973 - 2975
(2007/10/03)
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- Lewis acid assisted permanganate oxidations
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Lewis acids combine with permanganate in acetone solutions to form a complex that has enhanced oxidizing capabilities. The use of Lewis acids under these conditions to promote permanganate oxidations is superior to the use of Bronsted acids because the latter promote enolization of the solvent and subsequent unproductive reduction of the oxidant. The products obtained from a variety of alkenes, alkynes, arenes, sulfides, alcohols and ethers have been identified and probable reaction mechanisms proposed.
- Lai, Sheng,Lee, Donald G.
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p. 9879 - 9887
(2007/10/03)
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- The Mechanism of Enzymatic and Biomimetic Oxidations of Aromatic Sulfides and Sulfoxides
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Biomimetic and enzymatic oxidations of benzyl sulfides and sulfoxides lead to products (sulfoxides or sulfones) different from those obtained with bona fide electron transfer oxidations (products of C-H and/or C-S bond cleavage), which suggests the operation of an oxygen transfer machanism.
- Baciocchi, Enrico,Lanzalunga, Osvaldo,Marconi, Francesco
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p. 9771 - 9774
(2007/10/02)
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