Synthesis of Benzyltributylstannanes by the Reaction of N-Tosylhydrazones with Bu₃SnH

Abstract

An efficient stannylation process with N-tosylhydrazones or directly with carbonyl compounds has been developed. A series of functionalized benzyl- and alkyltributylstannanes can be synthesized in moderate to good yields under transition-metal-free conditions. Tandem transformations involving stannylation/Stille cross-coupling reaction have been carried out without purification of the benzyltributylstannane intermediates to afford a series of diarylmethane derivatives.

Luxury of N‐Tosylhydrazones in Transition‐Metal‐Free Transformations

“…[112] This metalfree stannylation process was extended to differently substituted aldehyde and ketoneh ydrazones,a ll giving moderate to good yields.T he lower yield in some cases was ascribed to the low stability of the al-kylstannanes upon column purification. [112] This metalfree stannylation process was extended to differently substituted aldehyde and ketoneh ydrazones,a ll giving moderate to good yields.T he lower yield in some cases was ascribed to the low stability of the al-kylstannanes upon column purification.…”

“…The final example discussed in this review is the synthesis benzyltributylstannanes 197 from N ‐tosylhydrazone and Bu 3 SnH which was achieved recently by Wang and co‐workers (Scheme ) . This metal‐free stannylation process was extended to differently substituted aldehyde and ketone hydrazones, all giving moderate to good yields.…”

Copper(I)/Bpy‐Catalyzed C‐2‐H Benzylation of Quinazolin‐4(3H)‐ones with N‐Tosylhydrazones

“…N ‐tosylhydrazones, which can be easily prepared from carbonyl compounds, have been widely used as the synthetic intermediates of diazo compounds or carbenes through the transition metal‐catalyzed or metal‐free reactions N ‐tosylhydrazone chemistry has widespread application in the construction of different types of C–X (X = C, N, O, S, P, Sn, and B) bonds in organic synthesis and various useful transformations. Recently, direct methods of Csp 3 –Csp 2 bonds formation by copper‐catalyzed benzylation of arenes and heteroarenes with N ‐tosylhydrazones have been developed as a versatile and efficient technique for C–H bond functionalization.…”

Copper‐catalyzed one‐pot coupling reactions of aldehydes (ketones), tosylhydrazide and 2‐amino(benzo)thiazoles: An efficient strategy for the synthesis of N‐alkylated (benzo)thiazoles

“…In recent years, the use of tosylhydrazones as important building blocks to achieve complex compounds has attracted more attention. Tremendous efforts were made by Barluenga et al ., Wang and co‐workers and others, who contributed valuable work on employing tosylhydrazones as versatile coupling partners to form various chemical bonds, including C–C, C–S, C–N, C–O, C–P, C–B, C–Sn, C–Si and N–N bonds. Despite many significant achievements, developing more efficient C–N bond formation methodologies utilizing tosylhydrazones is still required because this may offer new chances for the synthesis of bioactive compounds.…”