- Aza-Mannich condensation of sulfinimine promoted by tetrabutylammonium fluoride: Synthesis of α,β-unsaturated sulfinimine
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Self-condensation of tert-butanesulfinimine 5 was realized in the presence of tetrabutylammonium fluoride to afford α,β-unsaturated sulfinimine 8 in moderate to high yields with high geometric selectivities. The synthesized α,β-unsaturated sulfinimine 8 was demonstrated to be a versatile intermediate for the syntheses of enal 4 and chiral allyl amine 11. Georg Thieme Verlag Stuttgart.
- Bian, Xiaoxia,Zhang, Dan,Huang, Zhiyan,Qin, Yong
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- A Silyl Sulfinylamine Reagent Enables the Modular Synthesis of Sulfonimidamides via Primary Sulfinamides
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A new N-silyl sulfinylamine reagent allows the rapid preparation of a broad range of (hetero)aryl, alkenyl, and alkyl primary sulfinamides, using Grignard, organolithium, or organozinc reagents to introduce the carbon fragment. Treatment of these primary sulfinamides with an amine in the presence of a hypervalent iodine reagent leads directly to NH-sulfonimidamides. This two-step sequence is straightforward to perform and provides a modular approach to sulfonimidamides, allowing ready variation of both reaction components, including primary and secondary amines.
- Davies, Thomas Q.,Ding, Mingyan,Willis, Michael C.,Zhang, Ze-Xin
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supporting information
p. 1711 - 1715
(2022/03/14)
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- Hydroxylamine-Derived Reagent as a Dual Oxidant and Amino Group Donor for the Iron-Catalyzed Preparation of Unprotected Sulfinamides from Thiols
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An iron catalyzed reaction for the selective transformation of thiols (-SH) to sulfinamides (-SONH2) by a direct transfer of -O and free -NH2 groups has been developed. The reaction operates under mild conditions using a bench stable hydroxylamine derived reagent, exhibits broad functional group tolerance, is scalable and proceeds without the use of any precious metal catalyst or additional oxidant. This novel, practical reaction leads to the formation of two distinct new bonds (S=O and S?N) in a single step to chemoselectively form valuable, unprotected sulfinamide products. Preliminary mechanistic studies implicate the role of the alcoholic solvent as an oxygen atom donor.
- Chatterjee, Sayanti,Makai, Szabolcs,Morandi, Bill
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supporting information
p. 758 - 765
(2020/11/30)
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- Sulfinamide Synthesis Using Organometallic Reagents, DABSO, and Amines
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We report the synthesis of sulfinamides using organometallic reagents, a sulfur dioxide reagent, and nitrogen based-nucleophiles. The addition of an organometallic reagent to the commercially available sulfur dioxide surrogate, DABSO, generates a metal sulfinate which is reacted with thionyl chloride to form a sulfinyl chloride intermediate. Trapping the sulfinyl chlorides in situ with a variety of nitrogen nucleophiles delivers sulfinamides in 32-83% yields. Each stage of the process is performed at room temperature, and the total reaction time is only 1.5 h.
- Lo, Pui Kin Tony,Oliver, Gwyndaf A.,Willis, Michael C.
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p. 5753 - 5760
(2020/04/30)
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- Method for synthesizing tert-butyl sulfenamide
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The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for synthesizing tert-butyl sulfenamide. The invention aims to solve the problems of a long reaction route, a low reaction speed, a large amount of wastewater and application of a highly toxic product chlorine gas in the prior art. The method for preparing tert-butyl sulfinamide comprises the steps: (1) using tert-butyl disulfide as a starting material, and performing oxidative synthesis of tert-butyl sulfoxide tert-butyl ester under the action of a VO(acac)2 catalyst and hydrogen peroxide;and (2) performing bromination on the tert-butyl sulfoxide tert-butyl ester by using bromine in a solvent, and performing ammoniation by using ammonia water so as to obtain tert-butyl sulfenamide. The method has easily available raw materials, simple operation, safety and environmental protection, low cost and high yield, and is a suitable method for preparation of tert-butyl sulfenamide.
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Paragraph 0015; 0018-0026
(2019/08/20)
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- A synthetic method of a medicine raw material tert-butylsulfinamide
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The invention relates to a synthetic method of a medicine raw material tert-butylsulfinamide. The method includes subjecting sulfinamide and iso-butane which are raw materials to demethylation at 180-220 DEG C under 2-3 atmospheric pressures to generate the tert-butylsulfinamide. The method is simple, efficient, safe in operation and particularly practical in practical production.
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Paragraph 0006
(2016/12/01)
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- Approaches to 3,4,5-substituted piperidines via 1,2,5,6-tetrahydropyridines prepared by ring-closing metathesis
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Synthetic approaches to (1RS,2SR,6SR)-7-arylmethyl-2-alkoxymethyl-4,7-diaza-9-oxabicyclo[4.3.0]nonan-8-ones, potentially selective muscarinic M1 receptor agonists, by hydration of 1,2,5,6-tetrahydropyridines were investigated. 3-Substituted N-tosyl-1,2,5,6-tetrahydropyridines were prepared by ring-closing metathesis (RCM). The direct hydration of these by hydroboration-oxidation was not usefully selective, but cis-3-hydroxymethyl-4-tert-butyldimethylsilyloxy-N-tosylpiperidine was prepared from 3-hydroxymethyl-N-tosyl-1,2,5,6-tetrahydropyridine by epoxidation, mesylation, reductive elimination, silylation and hydroboration-oxidation. Problems were encountered during attempts to prepare 3-alkoxymethyl-1,2,5,6-tetrahydropyridines with protected amino and cyclobutyl substituents at C5 by ring-closing metathesis, perhaps because of steric hindrance. Nevertheless interesting chemistry was encountered during the synthesis of the RCM precursors including a novel coupling via a 2-ethenyl-N-nosylaziridine and the formation of an oxaazathiocin by an intramolecular substitution of the nitro group of an N-nosyl protected amine by a proximate hydroxyl substituent.
- Buffat, Maxime G.P.,Thomas, Eric J.
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p. 451 - 463
(2016/01/09)
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- Asymmetric synthesis of sulfinamides using (-)-quinine as chiral auxiliary
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A process has been designed and demonstrated for the asymmetric synthesis of sulfinamides using quinine as auxiliary. A variety of chiral sulfinamides including N-alkyl sulfinamides with diverse structure were prepared in good yields and excellent enantioselectivity starting from easily available and inexpensive reagents. The auxiliary quinine could be recovered and recycled.
- Zhang, Yongda,Chitale, Sampada,Goyal, Navneet,Li, Guisheng,Han, Zhengxu S.,Shen, Sherry,Ma, Shengli,Grinberg, Nelu,Lee, Heewon,Lu, Bruce Z.,Senanayake, Chris H.
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body text
p. 690 - 695
(2012/02/16)
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- 3-(2-Aminocarbonylphenyl)propanoic acid analogs as potent and selective EP3 receptor antagonists. Part 2: Optimization of the side chains to improve in vitro and in vivo potencies
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A series of 3-[2-{[(3-methyl-1-phenylbutyl)amino]carbonyl}-4-(phenoxymethyl)phenyl]propanoic acid analogs were synthesized and evaluated for their in vitro potency. In most cases, introduction of one or two substituents into the two phenyl moieties resulted in the tendency of an increase or retention of in vitro activities. Several compounds, which showed excellent subtype selectivity, were evaluated for their inhibitory effect against PGE2-induced uterine contraction in pregnant rats, which is thought to be mediated by the EP3 receptor subtype. The structure-activity relationships (SARs) are also discussed.
- Asada, Masaki,Iwahashi, Maki,Obitsu, Tetsuo,Kinoshita, Atsushi,Nakai, Yoshihiko,Onoda, Takahiro,Nagase, Toshihiko,Tanaka, Motoyuki,Yamaura, Yoshiyuki,Takizawa, Hiroya,Yoshikawa, Ken,Sato, Kazutoyo,Narita, Masami,Ohuchida, Shuichi,Nakai, Hisao,Toda, Masaaki
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experimental part
p. 1641 - 1658
(2010/04/29)
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- Ruthenium-catalysed asymmetric transfer hydrogenation of N-(tert-butanesulfinyl)imines
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The ruthenium complex prepared from [RuCl2(p-cymene)]2 and (1S,2R)-1-amino-2-indanol is a very efficient catalyst for the asymmetric transfer hydrogenation of (R)-N-(tert-butanesulfinyl)ketimines in isopropanol. By carefully removing
- Guijarro, David,Pablo, óscar,Yus, Miguel
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experimental part
p. 5386 - 5388
(2009/12/06)
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- The fate of the tert-butylsulfinyl auxiliary after acid-promoted cleavage-a method for recycling t-BuSONH2
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Ellman's chiral auxiliary is converted into tert-butylsulfinyl chloride on sulfinamide deprotection with HCl and can be recovered in high yield upon treatment with ammonia. The enantiopure auxiliary can be obtained by trapping the sulfinyl chloride with a chiral alcohol followed by treatment of the resulting sulfinate ester with LiNH2.
- Aggarwal, Varinder K.,Barbero, Nekane,McGarrigle, Eoghan M.,Mickle, Greg,Navas, Raquel,Suárez, José Ramón,Unthank, Matthew G.,Yar, Muhammad
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supporting information; experimental part
p. 3482 - 3484
(2009/09/28)
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- Recycling the tert-butanesulfinyl group in the synthesis of amines using tert-butanesulfinamide
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A practical process for recycling the tert-butanesulfinyl group upon deprotection of N-tert-butanesulfinyl amines has been achieved. Treatment of N-tert-butanesulfinyl amines with HCl in cyclopentyl methyl ether results in complete conversion to tert-butanesulfinyl chloride and the corresponding amine hydrochloride salt, which is isolated by filtration in analytically pure form and in quantitative yield. Treatment of the resulting sulfinyl chloride solution with aqueous ammonia then provides analytically pure tert-butanesulfinamide in 97% yield. Alternatively, the tert-butanesulfinyl chloride solution can be treated with ethanol and catalytic quinidine as a sulfinyl transfer catalyst to provide a cyclopentyl methyl ether solution of ethyl tert-butanesulfinate with 88% ee. Addition of NaNH2 in ammonia followed by simple trituration of the product with octane provides tert-butanesulfinamide with 99% ee and in 67% overall isolated yield based upon the starting N-tert-butanesulfinyl amine.
- Wakayama, Masakazu,Ellman, Jonathan A.
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experimental part
p. 2646 - 2650
(2009/08/15)
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- Subtilisin-catalyzed resolution of N-acyl arylsulfinamides
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We report the first biocatalytic route to sulfinamides (R-S(O)-NH 2), whose sulfur stereocenter makes them important chiral auxiliaries for the asymmetric synthesis of amines. Subtilisin E did not catalyze hydrolysis of N-acetyl or N-butanoyl arylsulfinamides, but did catalyze a highly enantioselective (E > 150 favoring the (R)-enantiomer) hydrolysis of N-chloroacetyl and N-dihydrocinnamoyl arylsulfinamides. Gramscale resolutions using subtilisin E overexpressed in Bacillus subtilis yielded, after recrystallization, three synthetically useful auxiliaries: (R)-p- toluenesulfinamide (42% yield, 95% ee), (R)-p-chlorobenzenesulfinamide (30% yield, 97% ee), and (R)-2,4,6-trimethylbenzenesulfinamide (30% yield, 99% ee). Molecular modeling suggests that the N-chloroacetyl and N-dihydrocinnamoyl groups mimic a phenylalanine moiety and thus bind the sulfinamide to the active site. Molecular modeling further suggests that enantioselectivity stems from a favorable hydrophobic interaction between the aryl group of the fast-reacting (R)-arylsulfinamide and the S1′ leaving group pocket in subtilisin E.
- Savile, Christopher K.,Magloire, Vladimir P.,Kazlauskas, Romas J.
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p. 2104 - 2113
(2007/10/03)
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- Chiral N-Acyl-tert-butanesulfinamides: The "Safety-Catch" Principle Applied to Diastereoselective Enolate Alkylations
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Diastereoselective enolate alkylation reactions of N-acylsulfmamides and conversion of the alkylation products to a variety of enantiopure products are reported. Several sulfinamides were prepared in solution followed by acylation to provide N-acylsulfmamides. The N-acylsulfinamides were then evaluated in diastereoselective enolate alkylation reactions. Of the sulfinamides evaluated, tert-butanesulfinamide provided the highest diastereoselectivity. To establish the potential utility of sulfinamides as versatile auxiliaries, methods were developed for (1) the racemization-free acylation of tert-butanesulfinamide to prepare optically pure N-acyl-tert-butanesulfinamides, (2) the diastereoselective C-alkylation of N-acyl-tert-butanesulfmamides, (3) the conversion of the N-acyl-tert-butanesulfmamides to the active ester equivalent by N-alkylation and S-oxidation, and (4) the cleavage of the N-alkyl-N-acyl-tert-butanesulfonamides to give chiral alcohol, ester, amide, and carboxylic acid target compounds. These studies provide the groundwork for the development of sulfinamides as dual chiral auxiliaries and linkers for the multistep solid-phase synthesis of enantioenriched compounds.
- Backes, Bradley J.,Dragoli, Dean R.,Ellman, Jonathan A.
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p. 5472 - 5478
(2007/10/03)
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