Synthesis of phthalan and phenethylamine derivatives via addition of alcohols to rhodium(II)-azavinyl carbenoids

Bennett, John M.; Shapiro, Jonathan D.; Choinski, Krystina; Mei, Yingbin; Aulita, Sky M.; Reinheimer, Eric W.; Majireck, Max M.

doi:10.1016/j.tetlet.2017.01.105

Cited by 14 publications

(4 citation statements)

References 104 publications

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“…A high functional‐group tolerance on the aryl ring was found ( 6 a – i ) in which alkyl, CF 3 , nitro, halogen, and even hydroxy group containing triazoles furnish vinyl triflates 6 in good yields and Z selectivities. In Rh II ‐catalyzed transformations of 1,2,3‐triazoles, the presence of a free OH group interfered with rhodium‐carbenoids . With alkene or nitrile additives (MeCN or 2‐methyl‐2‐butene, 10 equiv) our reaction was not affected, whereas in Rh‐catalyzed reactions transannulations took place.…”

Section: Figurementioning

confidence: 94%

“…In Rh II -catalyzed transformations of 1,2,3-triazoles, the presence of af ree OH group interferedw ith rhodium-carbenoids. [48,49] With alkene or nitrile additives (MeCN or 2-methyl-2-butene, 10 equiv)o ur re- www.chemeurj.org action was not affected, whereas in Rh-catalyzed reactions transannulations tookp lace. Additionally, N-sulfonyl 1,2,3-triazoles did not react with triflic acid in an analogousw ay to Nperfluoroalkyl triazoles but the main observed reactioni nt he former case was desulfonylation.…”

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confidence: 99%

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Stereoselective Synthesis of (Z)‐β‐Enamido Triflates and Fluorosulfonates from N‐Fluoroalkylated Triazoles

Markos

Voltrová

Motornov

et al. 2019

Chemistry A European J

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N-Fluoroalkylated 1,2,3-triazoles in the presence of triflic acid or fluorosulfonic acid underwentacascade reactionc onsisting of triazole protonation, ring opening, nitrogene limination, sulfonate addition, HF elimination, and hydrolysis to furnish novel trifluoromethanesulfonyloxy-or fluorosulfonyloxy-substituted enamides, respectively,i nahighly stereoselective fashion. The vinyl triflates underwent cross-coupling reactions to av ariety of substituted enamidesa nd serve as sourceso ft he aminovinyl cations. In reactions with triflic acid, electron-rich triazoles afforded2 -fluoroalkylated oxazoles. 2( CzechRepublic) [c] V. Motornov HigherChemical College, D. I. Mendeleev Universityo fthe Chemical Technologyo fRussia, Miusskaya sq.9,Moscow 125047 (Russia) Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.

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Section: Figurementioning

confidence: 94%

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confidence: 99%

Stereoselective Synthesis of (Z)‐β‐Enamido Triflates and Fluorosulfonates from N‐Fluoroalkylated Triazoles

Markos

Voltrová

Motornov

et al. 2019

Chemistry A European J

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“…Majireck and co-workers disclosed the Rh-catalyzed intramolecular cyclization of triazole-tethered benzyl alcohols to form N -(2-alkoxyvinyl)sulfonamide frameworks (Scheme ). Moreover, they converted the N -(2-alkoxyvinyl)sulfonamides to phenethylamine derivatives and substituted phthalan derivatives using simple synthetic transformations.…”

Section: Denitrogenative Transformations Of Triazolesmentioning

confidence: 99%

1,2,3-Triazole and Its Analogues: New Surrogates for Diazo Compounds

2022

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Readily accessible and shelf-stable 1,2,3-triazole and its analogues such as pyridotriazole, triazoloindole, benzotriazole, and thiadiazole exist in equilibrium with their ring-opened isomers, viz., diazo compounds. These ring-opened isomers could be trapped by various metal catalysts (e.g., Rh, Pd, Cu, Co, Ag, etc.) to generate the corresponding metal carbenoids with extrusion of nitrogen. As a consequence, these unique N-heterocycles facilitate access to a realm of N-containing complex structural motifs of biological importance through denitrogenative transformations such as transannulations, insertions, ylide formation, and rearrangements by trapping of the metal carbenoids with a diverse range of coupling partners (e.g., alkenes, alkynes, nitriles, carbo/heterocycles, X–H/C–X bonds, etc.). Hence, suitably substituted triazole derivatives have emerged as efficient surrogates of diazo compounds for the generation of reactive metal carbenoids during the past decades. In this comprehensive review, we aim to discuss in detail the remarkable advancement in their synthesis and synthetic applications.

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“…1,2,3,4,5,6,7,8,9,10 In particular, many novel uses of these intermediates for production of heterocycles 10 have provided chemists with new and efficient synthetic strategies. Toward this end, our group initiated development of a new protocol for the synthesis of phthalans 11 that would capitalize on recent advancements in the inter-and intramolecular additions of oxygen-based nucleophiles to Rh(II)-azavinyl carbenoids derived from N-sulfonyl-1,2,3-triazoles. 12,13,14,15,16,17 Our approach features a straightforward two-step protocol for converting terminal alkynes such as 1 into N-sulfonyl-1,2,3-triazoles 2 bearing a pendent alcohol (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

Preparation of <em>N</em>-(2-alkoxyvinyl)sulfonamides from <em>N</em>-tosyl-1,2,3-triazoles and Subsequent Conversion to Substituted Phthalans and Phenethylamines

Bennett

Shapiro

Choinski

et al. 2018

JoVE

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Decomposition of N-tosyl-1,2,3-triazoles with rhodium(II) acetate dimer in the presence of alcohols forms synthetically versatile N-(2-alkoxyvinyl)sulfonamides, which react under a variety of conditions to afford useful N- and O-containing compounds. Acid-catalyzed addition of alcohols or thiols to N-(2-alkoxyvinyl)sulfonamide-containing phthalans provides access to ketals and thioketals, respectively. Selective reduction of the vinyl group in N-(2-alkoxyvinyl)sulfonamide-containing phthalans via hydrogenation yields the corresponding phthalan in good yield, whereas reduction with sodium bis(2-methoxyethoxy)aluminumhydride generates a ring-opened phenethylamine analogue. Because the N-(2-alkoxyvinyl)sulfonamide functional group is synthetically versatile, but often hydrolytically unstable, this protocol emphasizes key techniques in preparing, handling, and reacting these pivotal substrates in several useful transformations.

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Synthesis of phthalan and phenethylamine derivatives via addition of alcohols to rhodium(II)-azavinyl carbenoids

Cited by 14 publications

References 104 publications

Stereoselective Synthesis of (Z)‐β‐Enamido Triflates and Fluorosulfonates from N‐Fluoroalkylated Triazoles

Stereoselective Synthesis of (Z)‐β‐Enamido Triflates and Fluorosulfonates from N‐Fluoroalkylated Triazoles

1,2,3-Triazole and Its Analogues: New Surrogates for Diazo Compounds

Preparation of <em>N</em>-(2-alkoxyvinyl)sulfonamides from <em>N</em>-tosyl-1,2,3-triazoles and Subsequent Conversion to Substituted Phthalans and Phenethylamines

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