期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 59, 期 20, 页码 7726-7731出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202000292
关键词
boryl anions; cycloaddition reactions; nucleophilic B-B bonds; organoboron clusters; Umpolung
资金
- Fonds der Chemischen Industrie Funding Source: Medline
The tetraaryl mu-hydridodiborane(4) anion [2H](-) possesses nucleophilic B-B and B-H bonds. Treatment of K[2H] with the electrophilic 9-H-9-borafluorene (HBFlu) furnishes the B-3 cluster K[3], with a triangular boron core linked through two BHB two-electron, three-center bonds and one electron-precise B-B bond, reminiscent of the prominent [B3H8](-) anion. Upon heating or prolonged stirring at room temperature, K[3] rearranges to a slightly more stable isomer K[3 a]. The reaction of M[2H] (M+=Li+, K+) with MeI or Me3SiCl leads to equimolar amounts of 9-R-9-borafluorene and HBFlu (R=Me or Me3Si). Thus, [2H](-) behaves as a masked [:BFlu](-) nucleophile. The HBFlu by-product was used in situ to establish a tandem substitution-hydroboration reaction: a 1:1 mixture of M[2H] and allyl bromide gave the 1,3-propylene-linked ditopic 9-borafluorene 5 as sole product. M[2H] also participates in unprecedented [4+1] cycloadditions with dienes to furnish dialkyl diaryl spiroborates, M[R(2)BFlu].
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