- Diversity-Oriented Synthesis of 1,2,4-Triazols, 1,3,4-Thiadiazols, and 1,3,4-Selenadiazoles from N-Tosylhydrazones
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The diversity-oriented synthesis of 1,2,4-triazols, 1,3,4-thiadiazols, and 1,3,4-selenadiazoles from N-tosylhydrazones was developed, and the reactions were general for a wide range of substrates, in which NH2CN, KOCN, KSCN, and KSeCN were used as odorless sources. Two different pathways were proposed, and N-tosylhydrazonoyl chlorides were formed in situ in the presence of NCS.
- Wei, Zeyang,Zhang, Qi,Tang, Meng,Zhang, Siyu,Zhang, Qian
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- Simple and efficient synthesis of pyrazole-fused porphyrins
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A simple and efficient method for the synthesis of pyrazole-fused porphyrins from readily available N-tosylhydrazones and 2-nitroporphyrins has been developed. This catalyst-free method can be applied to a wide range of substrates and demonstrate excellen
- Yang, Lei-Lei,Li, Xiao-Fang,Hu, Xiao-Lian,Yu, Xian-Yong
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- Visible-Light-Catalyzed in Situ Denitrogenative Sulfonylation of Sulfonylhydrazones
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A photocatalyzed in situ denitrogenative sulfonylation of N-arylsulfonyl hydrazones has been developed. This transformation provides a low-carbon strategy to assemble arylalkyl sulfones in a stepwise denitrogenation/sulfonylation manner.
- Huang, Xiang,Chen, Xing,Xie, Haisheng,Tan, Zheng,Jiang, Huanfeng,Zeng, Wei
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supporting information
p. 6784 - 6788
(2021/09/08)
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- Divergent Synthesis of Vinyl-, Benzyl-, and Borylsilanes: Aryl to Alkyl 1,5-Palladium Migration/Coupling Sequences
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Organosilicon compounds have been extensively utilized both in industry and academia. Studies on the syntheses of diverse organosilanes is highly appealing. Through-space metal/hydrogen shifts allow functionalization of C?H bonds at a remote site, which are otherwise difficult to achieve. However, until now, an aryl to alkyl 1,5-palladium migration process seems to have not been presented. Reported herein is the remote olefination, arylation, and borylation of a methyl group on silicon to access diverse vinyl-, benzyl-, and borylsilanes, constituting a unique C(sp3)?H transformation based on a 1,5-palladium migration process.
- Han, Jie-Lian,Ju, Cheng-Wei,Qin, Ying,Zhao, Dongbing
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supporting information
p. 6555 - 6560
(2020/03/03)
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- KI/TBHP-promoted [3 + 2] cycloaddition of pyrrolo[1,2-a]quinoxalines andN-arylsulfonylhydrazones
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An efficient KI/TBHP-promoted [3 + 2] cycloaddition of pyrrolo[1,2-a]quinoxalines andN-tosylhydrazones is described. A series of diverse fused [1,2,4]triazolo[3,4-c]quinoxalines was obtained in moderate to good yields with wide functional group tolerance.
- He, Jing,Li, Weiwei,Liu, Ping,Wei, Yueting,Yang, Zhen
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p. 3360 - 3366
(2020/05/14)
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- Base-Promoted Direct Synthesis of Sulfinates from N -Sulfonyl-hydrazones under Metal-Free Conditions
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A base-promoted direct synthesis of sulfinates from N -sulfonylhydrazones is described. Various N -sulfonylhydrazones, derived from aldehydes and ketones, are converted into the corresponding sulfinates in moderate to good yields. This protocol possesses
- Ji, Yuan-Zhao,Li, Hui-Jing,Luo, Dong-Hui,Wu, Qin-Xi,Wu, Yan-Chao
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p. 755 - 762
(2020/02/25)
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- Palladium-catalyzed cascade reactions of alkene-tethered carbamoyl chlorides with: N-tosyl hydrazones: Synthesis of alkene-functionalized oxindoles
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A palladium-catalyzed cascade reaction of alkene-tethered carbamoyl chlorides with N-tosyl hydrazones is described. It provided a new way to synthesize various alkene-functionalized oxindoles bearing an all-carbon quaternary center. The olefin moieties co
- Sun, Wan,Chen, Chen,Qi, Yuan,Zhao, Jinghui,Bao, Yinwei,Zhu, Bolin
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supporting information
p. 8358 - 8363
(2019/09/30)
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- Pyrazole synthesis via a cascade Sonogashira coupling/cyclization of N-propargyl sulfonylhydrazones
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An efficient approach for the preparation of pyrazoles via a Pd(ii)/Cu(i)-catalyzed Sonogashira coupling/cyclization of N-propargyl sulfonylhydrazones has been established. In this study, we firstly report the strategic use of a Sonogashira reaction to co
- Yang, Ying,Hu, Zi-Lin,Li, Ren-Hao,Chen, Yi-Hui,Zhan, Zhuang-Ping
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supporting information
p. 197 - 201
(2018/01/17)
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- Ring-Opening of Indoles: An Unconventional Route for the Transformation of Indoles to 1 H-Pyrazoles Using Lewis Acid
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An unusual transformation of indoles to pyrazoles via an aromatic ring-opening strategy has been developed. The salient feature of this strategy involves the C2-N1 bond opening and concomitant cyclization reaction of the C2=C3 bond of the indole moiety with the tosylhydrazone, which proceeds under transition-metal and ligand free conditions. This ring-opening functionalization of indoles provides a wide scope of differently substituted pyrazoles.
- Panda, Subhankar,Pradhan, Nirmalya,Manna, Debasis
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supporting information
p. 573 - 578
(2018/09/25)
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- One-Pot Acid-Catalyzed Ring-Opening/Cyclization/Oxidation of Aziridines with N-Tosylhydrazones: Access to 1,2,4-Triazines
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A new, three-step, telescoped reaction sequence for the regioselective conversion of N-tosyl hydrazones and aziridines to 3,6-disubstituted and 3,5,6-trisubstituted 1,2,4-triazines is described. The process involves an efficient nucleophilic ring opening of the aziridine, giving access to a wide range of aminohydrazones, isolated with excellent yields. A “one-pot” procedure, combining the ring opening with a cyclization and an oxidation step, allows the preparation of diversified triazines in good yields.
- Crespin, Lorène,Biancalana, Lorenzo,Morack, Tobias,Blakemore, David C.,Ley, Steven V.
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supporting information
p. 1084 - 1087
(2017/03/15)
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- A Transition-Metal-Free and Base-Mediated Carbene Insertion into Sulfur-Sulfur and Selenium-Selenium Bonds: An Easy Access to Thio- and Selenoacetals
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A transition-metal-free and base-mediated carbene insertion across sulfur-sulfur and selenium-selenium bonds has been developed by employing N-tosylhydrazone as a stable and safe carbene precursor. The ylide formation from carbene followed by Stevens rearrangement are considered to be the key steps. This thiol and selenol-free protocol delivers thioacetals and selenoacetals in good to excellent yields in short reaction time with good functional group tolerance. A one-pot synthesis involving in situ generation of tosylhydrazone has also been demonstrated. (Figure presented.).
- Arunprasath, Dhanarajan,Sekar, Govindasamy
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p. 698 - 708
(2017/02/23)
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- Highly stereoselective synthesis of 1-cyanocyclopropane-carboxamides from 3-substituted-2-cyanoacrylamides with N-tosylhydrazones under metal-free conditions
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A metal-free cyclopropanation of electron-deficient olefins 3-substituted-2-cyanoacrylamides with N-tosylhydrazones has been successfully developed. This strategy provide a simple route to the synthesis of very valuable 1-cyanocyclopropanecarboxamides wit
- Nie, Xufeng,Wang, Yachuan,Yang, Lijun,Yang, Zaijun,Kang, Tairan
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supporting information
p. 3003 - 3007
(2017/07/17)
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- Metal-Free Ring-Expansion Reaction of Six-membered Sulfonylimines with Diazomethanes: An Approach toward Seven-Membered Enesulfonamides
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A new metal-free, ring-expansion reaction of six-membered N-sulfonylimines with unstable diazomethanes, generated in situ from the N-tosylhydrazones, has been developed. This reaction delivers valuable seven-membered enesulfonamides by a Tiffeneau-Demjanov rearrangement and intramolecular proton transfer tautomerization process. Moreover, this ring-expansion reaction can be carried out in a one-pot fashion and scaled up to the gram scale by using aryl aldehydes, without the need to isolate the N-tosylhydrazone. A diazo thing: The title reaction between cyclic N-sulfonylimines and diazo compounds generated in situ from the N-tosylhydrazones is simple and functional-group tolerant. It thus delivers valuable seven-membered sulfonamides in up to 95 % yield. Moreover, this reaction can be carried out in one-pot starting from the aryl aldehydes, without the need to isolate the N-tosylhydrazone (right).
- Xia, An-Jie,Kang, Tai-Ran,He, Long,Chen, Lian-Mei,Li, Wen-Ting,Yang, Jin-Liang,Liu, Quan-Zhong
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supporting information
p. 1441 - 1444
(2016/02/12)
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- Iron(III) phthalocyanine-chloride-catalyzed synthesis of sulfones from sulfonylhydrazones
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In this study, sulfones are synthesized from sulfonylhydrazones catalyzed by iron(III) phthalocyanine chloride. This reaction offers broad substrate scope, occurs under mild conditions, utilized readily available reactants, and forms products in good-to-h
- Zhao, Jun-Long,Guo, Shi-Huan,Qiu, Jun,Gou, Xiao-Feng,Hua, Cheng-Wen,Chen, Bang
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supporting information
p. 2375 - 2378
(2016/05/19)
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- DERIVATIZATION OF CARBON
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Derivatization of an elemental carbon surface is accomplished by exposing the carbon surface to an aprotic solvent containing a hydrazone molecule of formula (I) or the corresponding salt of formula (II) wherein R1 is an organic group, and Rsu
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Paragraph 0038-0040
(2014/11/27)
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- An unprecedented approach to the Gabriel amine synthesis utilizing tosylhydrazones as alkylating agents
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A new and one-pot version of the Gabriel phthalimide amine synthesis utilizing carbonyl compounds as alkylating agents via their tosylhydrazone surrogates is disclosed. The alkylation involves copper catalysed carbene insertion into the N-H bond of phthalimide. Basically, the protocol also offers a powerful tool for deoxygenative hydroamination of carbonyl compounds.
- Yadav, Arvind K.,Yadav, Lal Dhar S.
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p. 34764 - 34767
(2014/11/08)
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- An easy access to fluoroalkanes by deoxygenative hydrofluorination of carbonyl compounds via their tosylhydrazones
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An efficient and operationally simple synthesis of fluoroalkanes by deoxygenative hydrofluorination of carbonyl compounds via their tosylhydrazone surrogates is reported. The reaction can be carried out in a one-pot procedure directly from carbonyl compounds.
- Yadav, Arvind K.,Srivastava, Vishnu P.,Yadav, Lal Dhar S.
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supporting information
p. 2154 - 2156
(2013/03/14)
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- N-Alkylation of tosylhydrazones in the presence of triphenylphosphine
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An efficient N-alkylation reaction of tosylhydrazones was developed in the presence of triphenylphosphine; triphenylphosphine played a key role in the transformation. A range of N-alkylated tosylhydrazones were prepared in good to high yields.
- Kong, Yuanfang,Zhang, Wen,Tang, Meng,Wang, Haiming
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supporting information
p. 7487 - 7491
(2013/08/23)
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- DABCO-promoted synthesis of pyrazoles from tosylhydrazones and nitroalkenes
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An efficient synthesis of pyrazoles from tosylhydrazones and nitroalkenes was developed. In comparison with the previously reported 1,3-dipolar cycloaddition reaction of diazo compounds with electron-deficient alkenes or alkynes, this methodology proceeded with a sequential Baylis-Hillman/ intramolecular cyclization mechanism and a variety of reversed regioselectivity products were prepared in good yields.
- Tang, Meng,Zhang, Wen,Kong, Yuanfang
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supporting information
p. 6250 - 6254
(2013/09/23)
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- Pd-catalyzed C=C double-bond formation by coupling of N-tosylhydrazones with benzyl halides
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Pd-catalyzed reaction of N-tosylhydrazones with benzyl halides affords di- and trisubstituted olefins In high yields with excellent stereoselectivity. This coupling reaction Is supposed to proceed through a migratory insertion of Pd carbene species.
- Xiao, Qing,Ma, Jian,Yang, Yang,Zhang, Yan,Wang, Jianbo
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supporting information; scheme or table
p. 4732 - 4735
(2009/12/24)
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- A new protocol for the in situ generation of aromatic, heteroaromatic, and unsaturated diazo compounds and its application in catalytic and asymmetric epoxidation of carbonyl compounds. Extensive studies to map out scope and limitations, and rationalization of diastereo- and enantioselectivities
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A variety of metalated tosylhydrazone salts derived from benzaldehyde have been prepared and were reacted with benzaldehyde in the presence of tetrahydrothiophene (THT) (20 mol %) and Rh2(OAc)4 (1 mol %) to give stilbene oxide. Of the lithium, sodium, and potassium salts tested, the sodium salt was found to give the highest yield and selectivity. This study was extended to a wide variety of aromatic, heteroaromatic, aliphatic, α,β-unsaturated, and acetylenic aldehydes and to ketones. On the whole, high yields of epoxides with moderate to very high diastereoselectivities were observed. A broad range of tosylhydrazone salts derived from aromatic, heteroaromatic, and α,β-unsaturated rated aldehydes was also examined using the same protocol in reactions with benzaldehyde, and again, good yields and high diastereoselectivities were observed in most cases. Thus, a general process for the in situ generation of diazo compounds from tosylhydrazone sodium salts has been established and applied in sulfur-ylide mediated epoxidation reactions. The chiral, camphor-derived, [2.2.1] bicyclic sulfide 7 was employed (at 5-20 mol % loading) to render the above processes asymmetric with a range of carbonyl compounds and tosylhydrazone sodium salts. Benzaldehyde tosylhydrazone sodium salt gave enantioselectivities of 91 ± 3% ee and high levels of diastereoselectivity with a range of aldehydes. However, tosylhydrazone salts derived from a range of carbonyl compounds gave more variable selectivities. Although those salts derived from electron-rich or neutral aldehydes gave high enantioselectivities, those derived from electron-deficient or hindered aromatic aldehydes gave somewhat reduced enantioselectivities. Using α,β-unsaturated hydrazones, chiral sulfide 7 gave epoxides with high diastereoselectivities, but only moderate yields were achieved (12-56%) with varying degrees of enantioselectivity. A study of solvent effects showed that, while the impact on enantioselectivity was small, the efficiency of diazo compound generation was influenced, and CH3CN and 1,4-dioxane emerged as the optimum solvents. A general rationalization of the factors that influence both relative and absolute stereochemistry for all of the different substrates is provided. Reversibility in formation of the betaine intermediate is an important issue in the control of diastereoselectivity. Hence, where low diastereocontrol was observed, the results have been rationalized in terms of the factors that contribute to the reduced reversion of the syn betaine back to the original starting materials. The enantioselectivity is governed by ylide conformation, facial selectivity in the ylide reaction, and, again, the degree of reversibility in betaine formation. From experimental evidence and calculations, it has been shown that sulfide 7 gives almost complete control of facial selectivity, and, hence, it is the ylide conformation and degree of reversibility that are responsible for the enantioselectivity observed. A simple test has been developed to ascertain whether the reduced enantioselectivity observed in particular cases is due to poor control in ylide conformation or due to partial reversibility in the formation of the betaine.
- Aggarwal, Varinder K.,Alonso, Emma,Bae, Imhyuck,Hynd, George,Lydon, Kevin M.,Palmer, Matthew J.,Patel, Mamta,Porcelloni, Marina,Richardson, Jeffery,Stenson, Rachel A.,Studley, John R.,Vasse, Jean-Luc,Winn, Caroline L.
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p. 10926 - 10940
(2007/10/03)
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- Chemoselective preparation of oximes, semicarbazones, and tosylhydrazones without catalyst and solvent
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A simple and versatile method for the synthesis of oximes, semicarbazones, and tosylhydrazones of aldehydes in the presence of ketones without catalyst and solvent is presented.
- Bandgar, Babasaheb P.,Sadavarte, Vaibhav S.,Uppalla, Lav S.,Govande, Rahul
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p. 403 - 406
(2007/10/03)
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- Alkylation of Aldehyde (Arenesulfonyl)hydrazones with Trialkylboranes
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(Arenesulfonyl)hydrazone derivatives of aryl aldehydes are readily alkylated by trialkylboranes in the presence of base to generate new organoboranes that may be converted to the corresponding substituted alkanes or alcohols depending upon the reaction conditions chosen. Both tosyl- and trisylhydrazone derivatives can be utilized in the reaction, which tolerates a variety of functional groups, making it a versatile alternative to both the Grignard and Suzuki-coupling reactions.
- Kabalka, George W.,Maddox, John T.,Bogas, Ekaterini,Kelley, Shane W.
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p. 3688 - 3695
(2007/10/03)
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- THE SYNTHESIS OF ARYL DIAZOMETHANES
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A convenient and rapid method for preparing aryldiazomethanes from the related tosylhydrazones employing phase transfer catalysis with hydrocarbon solvents in good to excellent yields has been developed.
- Wulfman, David S.,Yousefian, Shahram,White, Jon M
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p. 2349 - 2352
(2007/10/02)
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- Relationship between structure and antineoplastic activity of (arylsulfonyl)hydrazones of 4-pyridinecarboxaldehyde
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The effects of various structural modifications on the antineoplastic activity of (arylsulfonyl)hydrazones of 4-pyridinecarboxaldehyde were examined in mice bearing either Sarcoma 180 or P388 leukemia. The introduction of different functional groups into
- Shyam,Cosby,Sartorelli
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p. 149 - 152
(2007/10/02)
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