期刊
ACS CATALYSIS
卷 12, 期 20, 页码 13108-13115出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.2c03981
关键词
Hiyama-Denmark; tetrasubstituted-alkenes; vinyl silanes; palladium; cross-coupling
资金
- University of Delaware
- National Science Foundation [CHE-1254360, CHE-1800011, CHE-2102077]
- NSF [1247394]
- National Institute of Health Graduate Fellowship [T32GM133395]
- UNIDEL Foundation [18D]
- NIH [NSF CHE-0421224, CHE-0840401, CHE-1229234, NIH S10RR026962, P20GM104316, P30GM110758]
General conditions for the Hiyama-Denmark cross coupling of tetrasubstituted vinyl silanes and aryl halides are reported, enabling the coupling of unactivated vinyl silanes and displaying high stereospecificity. This important discovery simplifies the reaction procedure and reduces the use of toxic additives.
General conditions for the Hiyama-Denmark cross coupling of tetrasubstituted vinyl silanes and aryl halides are reported. Prior reports of Hiyama-Denmark reactions of tetrasubstituted vinyl silanes have required the use of vinyl silanols or silanolates, which are challenging to handle, or internally activated vinyl silanes, which lack structural generality. Now, unactivated tetrasubstituted vinyl silanes, bearing bench-stable tetraorganosilicon centers, and aryl halides can be coupled. The key to this discovery is the identification of dimethyl(5-methylfuryl)vinylsilanes as bench stable and easily prepared cross-coupling partners that are readily activated under mild conditions in Hiyama-Denmark couplings. These palladium-catalyzed cross-couplings proceed well with aryl chlorides, though aryl bromides and iodides are also tolerated, and the reactions display high stereospecificity in the formation of tetrasubstituted alkenes. In addition, only a mild base (KOSiMe3) and common solvents (THF/DMA) are required, and importantly, toxic additives (such as 18-crown-6) are not needed. We also show that these conditions are equally applicable to Hiyama-Denamrk coupling of trisubstituted vinyl silanes.
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