Development of methods for the sp2 C-H transformations of allenes has received much attention, and it presents a powerful tool for the synthesis of complicated allene-containing bioactive molecules. With a copper-catalyzed radical relay, the sp2 allenic C-H arylation and alkynylation were established herein, using various aryl boronic acids and trimethoxysilyl-substituted alkynes as carbon nucleophiles, and using electrophilic N-F reagents as nitrogen-centered radical precursors. These methods featured excellent site-selectivity to deliver fully substituted allenes efficiently. Moreover, with silyl-substituted allenes as substrates, a subsequential dual sp2 C-H functionalization process was established as well, which allowed for the divergent synthesis of multi-functionalized allenes, significantly expanding their chemical spaces. This result is published in JACS. Congratulations Zhongming Cheng.
We establish a remote hydrosulfonamidation (HSA) of alkenes using palladium catalysis, where N-fluoro-N-(fluoro-sulfonyl)-carbamate with a sulfur(VI) fluoride moiety is demonstrated as a good amidation reagent. The anti-Markovnikov HSA reaction of terminal alkenes and the remote HSA of internal alkenes are achieved to efficiently yield primary N-alkyl-N-(fluorosulfonyl)-carbamates. In addition, this protocol enables the high-value utilization of alkane by combining the dehydrogenation process. The generated N-alkyl products exhibit a unique reactivity of sulfur(VI) fluorides, which can be directly transferred to N-alkyl sulfamides or amines via the sulfur(VI) fluoride exchange reaction, thereby streamlining their synthesis. Moreover, a (pyridyl) benzazole-type ligand proved to be vital for the excellent chemo- and regioselectivities. This result is published in JACS. Congratulations Chanqi and Zhenye.
State Key Laboratory of Organometallic Chemistry
Shanghai Institute of Organic Chemistry, CAS
345 Lingling Lu, 200032 Shanghai, China
Office: Room 1305, Junmou Building
Phone: (+86) 021-54925346
Email: gliu@mail.sioc.ac.cn
Recruitment
Postdoctoral positions are available immediately in the Prof. Liu’s lab. Interested candidates with strong experimental experience on organic chemisty, especially on radical chemistry and transition metal catalysis, please submit a cover letter, Curriculum Vitae (including 2x references) and a short research summary to Prof. Liu, gliu@mail.sioc.ac.cn. Please put "Applications - Liu Group - PostDoc" in the subject line.
Postdoctoral positions are available immediately in the Prof. Liu’s lab. Interested candidates with strong experimental experience on organic chemisty, especially on radical chemistry and transition metal catalysis, please submit a cover letter, Curriculum Vitae (including 2x references) and a short research summary to Prof. Liu, gliu@mail.sioc.ac.cn. Please put "Applications - Liu Group - PostDoc" in the subject line.