Reaction of some 1-(p-tolylsulfonyl)-2,3,3-trialkyldiaziridines with aryl isocyanates and benzoyl isocyanate

Lehman, Laura S.; Baclawski, Leona M.; Harris, Stuart A.; Heine, Harold W.; Springer, James P.; Vandenheuvel, W.J.A.; Arison, Byron H.

doi:10.1021/jo00315a019

Cited by 10 publications

(6 citation statements)

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“…In order to explain the conversion of 3 to 6a, we propose the following mechanism (Scheme 4). In accord with previous contributions, 12,16,17 diaziridine 3 can ring open to form the azomethine imine 9. 18 The latter can undergo reaction with the alkyne 4a to produce the adduct 5a, which oxidatively aromatizes with loss of a proton; this step being favored in the presence of base (Table 4).…”

Section: Scheme 1 Synthesis Of Aroyldiaziridines Of 34-tetrahydroisosupporting

confidence: 85%

Facile Regioselective Synthesis of Pyrazolo[5,1-a]isoquinolines via Ring-Opening Cyclization/Oxidation Reactions of Stable Aroyldiaziridines of 3,4-Tetrahydroisoquinoline with Alkynes

Ortega¹,

Ahmed²,

Alper³

2007

Synthesis

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Newly prepared, stable aroyldiaziridines of 3,4-tetrahydroisoquinolines undergo regioselective cycloaddition reactions with a number of both mono and disubstituted alkynes, affording five-membered ring products which, after oxidative aromatization of the pyrazoline ring, lead to the efficient preparation of pyrazolo[5,1-a]isoquinolines. The overall transformation is base-catalyzed and occurs more rapidly in the presence of oxygen, in halogenated solvents and in dioxane.The employment of three-membered-ring heterocycles for the synthesis of five-membered-ring heterocycles has been widely used as a strategy for the preparation of a large number of compounds including some that are biologically active. 1 This approach was also used by our group for catalyzed 2-6 as well as uncatalyzed 6 reactions employing 1,2-and 1,2,3-substituted aziridines, 2 2-vinyloxiranes, 3 2-vinylaziridines, 4 2-vinylthiiranes 5 and 1,2-diaroyldiaziridines. 6 As part of our ongoing interest in the study of three-membered-ring compounds containing two heteroatoms, we investigated the reaction of alkynes with new, stable aroyldiaziridines of 3,4-tetrahydroisoquinoline to form five-membered-ring compounds which, on oxidative aromatization of the pyrazoline ring, gave pyrazolo[5,1-a]isoquinolines. Some pyrazoloisoquinolines and their derivatives are known to possess biological activity, such as antibiotics, 7 kinase inhibitors and anticonvulsants. 8,9 Although there are some reports on the reaction of diaziridines with acetylenes, 10-13 the utility of this reaction for the synthesis of five-membered-ring heterocycles has not been fully described. Thus far, there are no publications on the reactions of alkynes with stable aroyldiaziridines of 3,4-tetrahydroisoquinoline leading to the regioselective formation of pyrazolo[5,1-a]isoquinolines.Aroyldiaziridines of 3,4-tetrahydroisoquinoline 3 were prepared according to a slightly modified procedure 6 (Scheme 1).1,2,3,7b-Tetrahydro-1,1a-diazacyclopropa[a]naphthalene (1) 14 reacts with aroyl chlorides 2 in pyridine-benzene to give the aroyldiaziridines of 3,4-tetrahydroisoquinoline 3.To our knowledge, this is the first time that the aroyldiaziridines of 3,4-tetrahydroisoquinoline 3 have been synthesized as very stable, easy-to-handle, crystalline materials that do not decompose for months at room temperature.We investigated the reaction of aroyldiaziridines of 3,4-tetrahydroisoquinoline 3 with alkynes 4 under a range of conditions (Scheme 2). We noted that the reaction was rather slow when employing equimolar amounts of reactants at room temperature; thus, we increased the temperature and the concentration of the alkyne 4a in order to accelerate the formation of 5a.Scheme 2 Cycloaddition reaction of 3,4-tetrahydroisoquinoline (3a) with phenylacetylene (4a) The structure of the cycloaddition product 5a was confirmed by single-crystal X-ray diffraction (Figure 1). 15 During handling of the colorless crystals of 5a, we noticed that some small but noticeable transformation to a light yellow compound was ta...

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Section: Scheme 1 Synthesis Of Aroyldiaziridines Of 34-tetrahydroisosupporting

confidence: 85%

Facile Regioselective Synthesis of Pyrazolo[5,1-a]isoquinolines via Ring-Opening Cyclization/Oxidation Reactions of Stable Aroyldiaziridines of 3,4-Tetrahydroisoquinoline with Alkynes

Ortega¹,

Ahmed²,

Alper³

2007

Synthesis

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“…1, there are two crystallographically independent molecules in the asymmetric unit. Most bond lengths and angles in (I) are within normal ranges with the geometries around S atom being distorted tetrahedra (Lehman et al, 1981;Starilkova et al, 1982), with two O atoms, one N and C atom.…”

Section: S1 Commentmentioning

confidence: 98%

“…For the chemistry of sulfonamides, see: Yin et al (2007). For geometry, see: Lehman et al (1981); Starikova et al (1982); Bernstein et al (1995); Etter (1990). 1999.9 (3) Å 3 Z = 8 Mo K radiation = 0.32 mm À1 T = 298 (2) K 0.27 Â 0.13 Â 0.11 mm…”

Section: Related Literaturementioning

confidence: 99%

2-(4-Methylphenylsulfonamido)acetic acid

He¹,

Ma²,

Lin³

et al. 2007

Acta Cryst E

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Key indicators: single-crystal X-ray study; T = 298 K; mean (C-C) = 0.010 Å; R factor = 0.056; wR factor = 0.113; data-to-parameter ratio = 12.8.In the title compound, C 9 H 11 O 4 NS, there are two crystallographically independent molecules in the asymmetric unit. The S atoms are in a distorted tetrahedral configuration. Symmetry-related molecules are linked to form dimers via O-HÁ Á ÁO hydrogen bonding, and the dimers are associated to form infinite chains via N-HÁ Á ÁO hydrogen bonding.There are close C-HÁ Á ÁO approaches of 3.342 (7) and 3.353 (7) Å between the two independent molecules.Experimental Crystal data C 9 H 11 NO 4 S M r = 229.26 Monoclinic, P2 1 =c a = 22.3240 (19) Å b = 5.7263 (5) Å c = 16.5526 (14) Å = 109.069 (2) V = 1999.9 (3) Å 3 Z = 8 Mo K radiation = 0.32 mm À1 T = 298 (2) K 0.27 Â 0.13 Â 0.11 mm Data collection Bruker APEX area-detector diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2000) T min = 0.919, T max = 0.956 9980 measured reflections 3524 independent reflections 2969 reflections with I > 2(I) R int = 0.049

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“…

Heating 6-aryl-1,5-diazabicyclo[3.1.0]hexanes in the presence of aryl isocyanates or aryl isothiocyanates leads to the formation of the corresponding 2,3-diarylperhydropyrazolo[1,2-a][1,2,4]triazol-1-one or 2,3-diarylperhydropyrazolo[1,2a] [1,2,4]triazol-1-thione in good yield as a result of 1,3-dipolar cycloaddition of isocyanate (isothiocyanate) to an initially formed ylide.

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mentioning

confidence: 99%

“…1,2 On the other hand, diaziridines containing no electron-withdrawing groups near to the nitrogen atoms, e.g., 1,2,3-triethyldiaziridine can directly react with phenyl isocyanate to form a number of products with a formal nitrogen-nitrogen bond cleavage in low yields. 1,2 On the other hand, diaziridines containing no electron-withdrawing groups near to the nitrogen atoms, e.g., 1,2,3-triethyldiaziridine can directly react with phenyl isocyanate to form a number of products with a formal nitrogen-nitrogen bond cleavage in low yields.…”

mentioning

confidence: 99%

Reaction of 6-Aryl-1,5-diazabicyclo[3.1.0]hexanes with Aryl Isocyanates and Aryl Isothiocyanates

2000

Synlett

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Reaction of some 1-(p-tolylsulfonyl)-2,3,3-trialkyldiaziridines with aryl isocyanates and benzoyl isocyanate

Cited by 10 publications

References 0 publications

Facile Regioselective Synthesis of Pyrazolo[5,1-a]isoquinolines via Ring-Opening Cyclization/Oxidation Reactions of Stable Aroyldiaziridines of 3,4-Tetrahydroisoquinoline with Alkynes

Facile Regioselective Synthesis of Pyrazolo[5,1-a]isoquinolines via Ring-Opening Cyclization/Oxidation Reactions of Stable Aroyldiaziridines of 3,4-Tetrahydroisoquinoline with Alkynes

2-(4-Methylphenylsulfonamido)acetic acid

Reaction of 6-Aryl-1,5-diazabicyclo[3.1.0]hexanes with Aryl Isocyanates and Aryl Isothiocyanates

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