- 作者: 張昭菀、林英智
- 作者服務機構: Department of Chemistry, National University Preparatory School for Overseas Chinese Students, Linkou, Taipei Hsien, 244, Taiwan, R.O.C.
- 中文摘要: Treatment of [Ru]CoCPh (1, [Ru] = (h5-C5H5)(dppe)Ru, dppe = Ph2PCH2CH2PPh2) with PhN=C=S at room temperature affords the [2 + 2] cycloaddition product [Ru]-C=C(Ph)C(=NPh)S (2) which contains a four-membered-ring heterocycle. A series of cationic S-alkylated ruthenium vinylidene complexes [Ru]=C=C(Ph)C(=NPh)SCH2R+ (3a, R = CONH2; 3b, R = CH=CH2; 3c, R = p-C6H4CF3) and N-alkylated ruthenium vinylidene complexes [Ru]=C=C(Ph)C(=S)N(Ph)CH2R+ (4b, R = CH=CH2; 4c, R = p-C6H4CF3) are prepared from 2 with organic halides at room temperature with high yields. Deprotonation of 3a and 3c by n-Bu4NOH in acetone induces novel cyclization reactions via C-C bond formation and yields neutral five-membered-ring heterocyclic complexes [Ru]-C=C(Ph)C(=NPh)SCHR (5a, R = CONH2; 5c, R = p-C6H4CF3). In a similar manner, deprotonation of 4b and 4c by NaOMe in CH2Cl2 also induces another cyclization to yield the pyrrole-2-thione complexes [Ru]-C=C(Ph)C(=S)N(Ph)CHR (6b, R = CH=CH2; 6c, R = p-C6H4CF3). At room temperature, 5c isomerizes to the 2-aminothiophene complex [Ru]-C=C(p-C6H4CF3) SC(NHPh)=C(Ph) (7c) in solution.
- 英文摘要: --
- 中文關鍵字: Deprotonation-induced cyclization; N-Alkylation vinylidene; S-Alkylation vinylidene; Five-membered ring; Heterocyclic; 2-Aminothiophene; Pyrrole-2-thione.
- 英文關鍵字: Deprotonation-induced cyclization; N-Alkylation vinylidene; S-Alkylation vinylidene; Five-membered ring; Heterocyclic; 2-Aminothiophene; Pyrrole-2-thione.