Elsevier

Tetrahedron Letters

Volume 59, Issue 45, 7 November 2018, Pages 4019-4023
Tetrahedron Letters

Synthesis of arylstannanes by palladium-catalyzed desulfitative coupling reaction of sodium arylsulfinates with distannanes

https://doi.org/10.1016/j.tetlet.2018.09.065Get rights and content

Highlights

  • Pd-catalyzed desulfitative cross-coupling reaction of sodium arylsulfinates with hexaalkyl distannanes is realized.

  • Readily available sodium arylsulfinates are used as the substrates.

  • This reaction features low catalyst loading, good functional groups tolerance, moderate to excellent yields.

  • Gram-scale synthesis and tandem Stille coupling reactions are successfully implemented.

Abstract

A novel Pd-catalyzed desulfitative cross-coupling reaction of sodium arylsulfinates with hexaalkyl distannanes is realized, allowing the facile synthesis of functionalized arylstannanes with moderate to excellent yields. The successful implement of gram-scale synthesis and tandem Stille coupling reaction demonstrates the potential applications of this method in organic synthesis.

Introduction

Organotin reagents, especially for arylstannanes derivatives, have been found great applications in organic synthesis and other fields [1]. In particular, the Stille coupling reaction, in which the essence is the cross-coupling reaction with organotin reagents, is rapidly becoming a powerful synthetic strategy for selective Csingle bondC bond formation [2]. Particularly, compared with Suzuki-Miyaura reactions, the Stille coupling methodology has been found to be highly effective for synthesizing functional materials [1j]. Moreover, aryl C-Sn bond can further be applied in functional group transformations, including Csingle bondN [3], Csingle bondF [4], Csingle bondOCF3 [5], and C–B bond [6] formation. The wide application has created considerable need for the easy access to aryl stannane derivatives. However, the synthetic methods for accessing arylstannane compounds are still limited. The most commonly used strategy to synthesize functionalized aryl stannanes is the reaction of trialkyl tin halide with aromatic metal reagents, including aryl magnesium, -lithium, or -zinc reagents (Scheme 1a) [7]. Alternative methods are the aromatic nucleophilic substitution between aryl halides or ammonium salts and trialkyl stannyl anion (Scheme 1b) [8]. In addition, Pd-catalyzed cross-coupling reaction from aryl halides/ArOTf with distannanes has been developed (Scheme 1c) [9]. Moreover, the radical type stannylation of aryl diazonium salts or aryl iodides are carried out under transition-metal-free condition (Scheme 1d) [10]. Recently, the Ni-catalyzed stannylation reactions of aryl esters were developed by Martín [11a] and Rueping [11b], using silylstannyl derivatives and distannanes as the stannylation reagents respectively (Scheme 1e).

Arylsulfinic acids or their arylsulfinate salts, which can be conveniently synthesized from the corresponding aryl sulfonyl halides, have played important role as versatile intermediates in organic synthesis because of their readily availability, air stability and low price [12]. In addition to participating in sulfonylation reactions [13], arylsulfinic acids or sodium arylsulfinates can be served as novel alternatives for transition-metal-catalyzed desulfitative Csingle bondC bond formations by releasing SO2 [14]. As a new strategy of aryl sources, the importance of desulfitative coupling reactions has been adequately proved in Heck-type reactions [15], synthesis of biaryls [16], synthesis of aryl ketones [17] and Csingle bondH bond arylation [18]. However, desulfitative coupling reaction of arylsulfinates for constructing carbon-heteroatom bond still remains great challenge. Recently, Wang and Xiao have reported the novel Pd-catalyzed desulfitative Csingle bondP coupling of sodium arylsulfinates respectively [19a,b]. The Cu-promoted desulfitative N-arylation with sodium arylsulfinates was also explored [19c]. Based on our interests in desulfitative coupling reactions and the importance of aryl stannane reagents, herein we report the desulfitative cross-coupling reaction of sodium aryl sulfinates with hexabutyldistannane under palladium catalysis (Scheme 1f).

Section snippets

Results and discussion

At the outset, we started our investigation by examining Pd(PPh3)2Cl2 catalyzed cross-coupling reaction of sodium benzenesulfinate 1a with hexabutyldistannane 2a in the presence of Ag2CO3 in DMF at 60 °C. To our disappointment, only a trace amount of product 3a could be detected (entry 1). Subsequently, the reaction temperature was raised and the yield improved to 44% (entry 2, 3). Various palladium catalysts were examined at 110 °C, and Pd(PtBu3)2 was found as the best catalyst in this

Conclusion

In conclusion, we have developed a new synthetic method towards trialkyl arylstannanes through Pd-catalyzed desulfitative cross-coupling reaction of sodium aryl sulfinates with distannanes. The reaction features high efficiency with low catalyst loading, good functional groups tolerance, affording stannylation products with moderate to excellent yields. Besides, the starting materials are easily prepared from the corresponding aryl sulfonyl chlorides. Because of the importance of arylstannane

Acknowledgments

This work is supported by the scientific research funding of Tianjin Normal University (5RL138), National Natural Science Foundation of China (21602156), and Shanghai Sailing Program (18YF1401800).

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