81740-70-7Relevant academic research and scientific papers
Complementary iron(II)-catalyzed oxidative transformations of allenes with different oxidants
Sabbasani, Venkata R.,Lee, Hyunjin,Xia, Yuanzhi,Lee, Daesung
supporting information, p. 1151 - 1155 (2016/01/20)
Substituent- and oxidant-dependent transformations of allenes are described. Given the profound influence of the substituent on the reactivity of allenes, the subtle differences in allene structures are manifested in the formation of diverse products when reacted with different electrophiles/oxidants. In general, reactions of nonsilylated allenes involve an allylic cation intermediate by forming a C-O bond, at the sp-hybridized C2, with either DDQ (2,3-dichloro-5,6-dicyano-p-benzoquinone) or TBHP (tert-butyl hydroperoxide), along with FeCl2·4 H2O (10 mol %). In contrast, silylated allenes favor the formation of propargylic cation intermediates by transferring the allenic hydride to the oxidant, thus generating 1,3-enynes (E1 product) or propargylic THBP ethers (SN1 product). The formation of these different putative cationic intermediates from nonsilylated and silylated allenes is strongly supported by DFT calculations. Profound impact: Iron(II)-catalyzed transformations of allenes induced by either DDQ or tBuOOH depend on the substituent on the allenes. Nonsilylated and silylated allenes show complementary reactivity upon exposure to DDQ and tBuOOH in the presence of an iron(II) catalyst. Nonsilylated allenes incorporate the oxidant at the sp-hybridized carbon, whereas the silylated allenes generate 1,4-dehydrogenated 1,3-enynes. DDQ=2,3-dichloro-5,6-dicyano-1,4-benzoquinone.
(Thioallyl)iron tricarbonyl complexes
Choi, Nami,Kabe, Yoshio,Ando, Wataru
, p. 1506 - 1513 (2008/10/08)
The tetramethylallene episulfide la reacts with Fe2(CO)9 to afford (tetramethylthioallyl)iron tricarbonyl complex 2a and (μ-2,4-dimethyl-2-pentene-3,4-dithioiato-κ2S:κ 2S′)diiron hexacarbonyl (3). The structure of 3 was characterized crystallographically. The reaction of 1-tert-butyl-3,3-diphenylallene 1-episulfide (1b) with Fe2(CO)9 resulted in the formation of (1-tert-butyl-3,3-diphenyl-2-thioallyl)iron tricarbonyl (2b). The (thioallyl)iron tricarbonyl complex 2b exists as an η4-π-complex as revealed by 1H and 13C NMR spectroscopy as well as by X-ray diffraction analysis. Thermolysis of 2b in the presence of carbon monoxide gave 2-tert-buyl-4-(diphenylmethylidene)thietan-3-one (7). Complex 2b reacts with PPh3 to give 7 and metalathiopentanone 8. Heating of 8 gave 7 and a corresponding allene 5b. According to the structure of 7 and 8 and chemical observations, thermolysis of 8 took place to give 7 via a metathesis-like reaction of 1,2- or 1,3-metalathietane 13 and 15.
Formation of thioruthenium carbonyl clusters via a thioallyl cation complex
Choi, Nami,Kabe, Yoshio,Ando, Wataru
, p. 607 - 613 (2008/10/08)
Tetramethylallene episulfide (1a) reacts with Ru3(CO)12 to afford the oxidative addition hydride clusters Ru3(CO)10[μ-S(C=CMe2)C(Me)=CH 2](μ-H) (2) and Ru3(CO)9[μ-S(C=CMe2)C(Me)=CH 2](μ-H) (3), respectively. The structure of 2 was characterized crystallographically. The cluster 2 undergoes decarbonylation at 60°C to form 3 in 47% yield. The cluster 3 can regenerate 2 by bubbling with carbon monoxide under 1 atm of pressure at room temperature, in 80% yield. The chemical correlations leave little doubt about the structure of 3 which has a six-electron donating (μ-S)(μ-H)η2-dimethylpentadiene ligand. The reaction of 1-tert-butyl-3,3-diphenylallene 1-episulfide (1b) with Ru3(CO)12 resulted in the formation of the cluster Ru3(CO)10[2-(μ-S)-1-tert-butyl-3-phenylindene](μ-H) (5). The X-ray structure of 5 shows that intramolecular cyclization has occurred besides C-S bond cleavage. The thioallyl cation complexes 9 and 10 are the intermediates of the formation of clusters 2 and 5. Upon warming to 80-120°C, 2 and 5 were finally converted to desulfurized products 2,4-dimethyl-1,3-pentadiene (6) (quantitative) and 1-tert-butyl-3-phenylindene (7) (56%) along with thio cluster HRu5(CO) 15[2-(μ-S)-1-tert-butyl-3-phenylindene](μ4-S) (8) (30%).
