title: Intramolecular C-F and C-H bond cleavage promoted by butadienyl heavy Grignard reagents.
abstract: Organomagnesium compounds (Grignard reagents) are among the most useful organometallic reagents and have greatly accelerated the advancement of synthetic chemistry and related sciences. Nevertheless, heavy Grignard reagents based on the metals calcium, strontium or barium are not widely used, mainly due to their rather inert heavy alkaline-earth metals and extremely high reactivity of their corresponding Grignard-type reagents. Here we report the generation and reaction chemistry of butadienyl heavy Grignard reagents whose extremely high reactivity is successfully tamed. Facile synthesis of perfluoro-π-extended pentalene and naphthalene derivatives is realized by the in situ generated heavy Grignard reagents via intramolecular C-F/C-H bond cleavage. These obtained perfluorodibenzopentalene and perfluorodinaphthopentalene derivatives show low-lying LUMO levels, with one being the lowest value so far among all pentalene derivatives. Our results set an exciting example for the meaningful synthetic application of heavy Grignard reagents.
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Haidian, Beijing 100871, China.
authors.forename: Heng
authors.initials: H
authors.lastname: Li
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Haidian, Beijing 100871, China.
authors.forename: Xiao-Ye
authors.initials: XY
authors.lastname: Wang
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Haidian, Beijing 100871, China.
authors.forename: Baosheng
authors.initials: B
authors.lastname: Wei
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Haidian, Beijing 100871, China.
authors.forename: Ling
authors.initials: L
authors.lastname: Xu
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Haidian, Beijing 100871, China.
authors.forename: Wen-Xiong
authors.initials: WX
authors.lastname: Zhang
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Haidian, Beijing 100871, China.
authors.forename: Jian
authors.initials: J
authors.lastname: Pei
authors.affiliation: 1] Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Haidian, Beijing 100871, China [2] State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, CAS, Shanghai 200032, China.
authors.forename: Zhenfeng
authors.initials: Z
authors.lastname: Xi