کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1325135 1499854 2015 10 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
What factors cause the complete substrate-controlled selectivity in Rh2(Piv)4-catalyzed cycloadditions of 1,2,3-triazoles with isocyanates or isothiocyanates
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی معدنی
پیش نمایش صفحه اول مقاله
What factors cause the complete substrate-controlled selectivity in Rh2(Piv)4-catalyzed cycloadditions of 1,2,3-triazoles with isocyanates or isothiocyanates
چکیده انگلیسی


• Cycloaddition mechanisms of 1,2,3-triazoles with isocyanates/isothiocyanates were studied.
• The nucleophilic trend (CS > CN > CO) is the main selective origin of these reactions.
• The presence of Rh2(Piv)4 is another selective origin via stabilizing azavinyl carbene.

DFT studies on Rh2(Piv)4-catalyzed cycloadditions of 1,2,3-triazoles with isocyanates or isothiocyanates show that 1, 2, 3-triazoles undergo ring opening → coordination of Rh2(Piv)4 → dissociation of N2 to give Rh2(Piv)4-azavinyl carbene, where Rh2(Piv)4 exerts a stabilizing effect on azavinyl carbene. The formed Rh2(Piv)4-azavinyl carbene prefers to nucleophilically cyclize with CN bond of isocyanatobenzene to give the imidazolone, rather than CO bond of isocyanatobenzene to give the oxazolimine. In comparison, Rh2(Piv)4-azavinyl carbene preferentially cyclize with CS bond of isothiocyanatobenzene to give the thiazole, instead of CN bond of isothiocyanatobenzene to give the thioimidazolone. The nucleophilic capacity follows CS > CN > CO trend, which is the key selective origin of these reactions. The presence of Rh2(Piv)4 would help to form the carbene and to stabilize it via donating its d-electron into the azavinyl carbene, which is another selective origin of these reactions.

Rh2(Piv)4-azavinyl carbene nucleophilically cyclizes with isocyanatobenzene to give imidazolone, while with isothiocyanatobenzene to give thiazole. The nucleophilic capacity follows CS > CN > CO trend, which is main selective origin of these reactions. The presence of Rh2(Piv)4 help to form the carbene and to stabilize it, which is another selective origin.Figure optionsDownload as PowerPoint slide

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Organometallic Chemistry - Volume 788, 15 July 2015, Pages 58–67
نویسندگان
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