Mild and selective silicon-mediated access to enantioenriched 1,2-mercaptoamines and β-amino arylchalcogenides

Abstract

Metal-free ring opening reactions of activated and unactivated aziridines with different silyl chalcogenides are described.

Ring opening reactions of heterocycles with selenium and tellurium nucleophiles

“…27 Recently, in order to disclose novel ring-opening-based protocols for the synthesis of functionalised organotellurides, we extended the scope of the reactivity of silyl tellurides to aziridines and thiiranes (Schemes 12 and 13). 28,29 The NRORs occurred with stereospecificity and excellent regioselectivity in the presence of TBAF. ArX Ph 7r, Ar = p-Tol, X = Se, 55% 8j, Ar = p-Tol, X = Te, 69% 15d, Ar = p-Tol, X = S, 56% 15e, Ar = m -Br-C 6 H 4 , X = S, 58% Scheme 13: Synthesis of β-arylchalcogeno amines through NRORs of aziridines with silyl chalcogenides.…”

Unexpected Ethyltellurenylation of Epoxides with Elemental Tellurium under Lithium Triethylborohydride Conditions

“…During the course of our studies on the reactivity of strained heterocycles with selenium-centered nucleophiles we developed convenient routes towards generating a variety of hydroxy-, amino-, and mercapto-substituted Se-containing systems [50][51][52][53]. For example, through the tuning of the stoichiometry and the conditions of the reaction of (Me 3 Si) 2 Se [(bis(trimethylsilyl)selenide, a synthetic equivalent of hydrogen selenide] with epoxides, thiiranes, and aziridines, we were able to successfully achieve a range of functionalised selenols [50], selenides, and diselenides [47].…”

gem-Heterosubstituted (stannyl)methylsilanes as synthetic equivalents of functionalized α-stannyl(methyl) anions

“…16,32 In this scenario, we recently reported new synthetic procedures for the synthesis of selenium-containing functionalized small molecules under mild conditions. [33][34][35] However, despite the interest in the synthesis of organoselenium compounds, to the best of our knowledge, no reports are available on the -metalation of selenyl derivatives. In fact, treatment of selenides with an alkyllithium generally leads to an easy metal-lithium exchange, thus hampering the formation of carbanions, unless suitable substrates are used.…”

“…C NMR (CDCl3, 50 MHz), δ (ppm): 10.8, 13.7, 14.0, 27.3, 29.0, 38.4, 74.4, 125.3, 127.1, 128.2, 129.2, 131.0, 133.0, 142.9. MS: m/z (%) 260(35), 179 (79), 165(24), 102 (85), 91(26), 77 (100), 51 (51). Elemental analysis: C26H40OSeSn Calcd.…”