ISSN:
1434-1948
Keywords:
Enolates
;
Nucleophilic additions
;
Ruthenium
;
S ligands
;
Sulfenes
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Reaction of the chiral racemic complex [CpRu(mppe)(SO2)]PF6 (1, mppe = Me2PC2H4PPh2) with diazomethane or -ethane gave the sulfene complexes [CpRu(mppe)(RHC/SO2)]PF6 (R = H, 2a; R = Me, 2b). Treatment of 2a with prochiral enamines or deprotonated β-oxo esters yielded C-C coupling products with 32-60% de. An analog of 2a, [NmcpRu(mppe)(H2C/SO2)]PF6 (8, Nmcp = neomenthylcyclopentadienyl) was prepared in a four-step synthesis starting from LiNmcp and [RuCl2(PPh3)3]. Repeated crystallization of the intermediate [NmcpRu(mppe)Cl] (6) provided diastereomerically pure 6′ which added methylene stereospecifically to give diastereomerically pure 8′. Compound 8 turned out to be much less reactive towards nucleophiles than 2a, but still added deprotonated ethyl 2-methyl-3-oxobutanoate with 44% de. The chiral, enantiomerically pure sulfur dioxide complex [CpRu(chir)(SO2)]PF6 [10, chir = (S,S)-Ph2PCHMeCHMePPh2] was synthesized from [CpRu(chir)Cl] and SO2 and was characterized by X-ray crystallography. Reaction of 10 with diazomethane gave the enantiomerically pure sulfene complex [CpRu(chir)(H2C/SO2)]PF6 (11). Addition reactions of 11 with N-(1-cyclopentenyl)morpholine, as well as with various enolates derived from β-oxo esters or 1,3-diesters proceeded with high yields and 20-90% de. The structure of a diastereomerically pure addition product, [CpRu(chir)(SO2CH2C(Me){C(O)Me}{C(O)OtBu}] (13d′), was determined crystallographically and was shown to have (R) configuration at the quaternary carbon atom. After alkylation of one of the S/O functions, the sulfinate ligand was cleaved from the metal center by ligand substitution with acetonitrile, and the resulting acetonitrile complex 15 was converted back into 10 by treatment with SO2.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
