Detail of "5674-01-1"

Reference

Planar Trimethylenemethane Dianion Chemistry of Lanthanide Metallocenes: Synthesis, Structure, Density Functional Theory Analysis, and Reactivity of [(C5Me5)2Ln]2[m-h3:h3-C(CH2)3] Complexes

All Rights Reserved. Planar Trimethylenemethane Dianion Chemistry of Lanthanide Metallocenes: Synthesis, Structure, Density Functional Theory Analysis, and Reactivity of [(C5Me5)2Ln]2[m-h3:h3-C(CH2)3] Complexes. Evans, William J.; Champagne, Timothy M.; Ziller, Joseph W.; Kaltsoyannis, Nikolas (Department of Chemistry, University of California, Irvine, CA 92697-2025, USA). Journal of the American Chemical Society, 128(50), 16178-16189 (English) 2006 American Chemical Society. CODEN: JACSAT. ISSN: 0002-7863. DOCUMENT TYPE: Journal CA Section: 29 (Organometallic and Organometalloidal Compounds) Section cross-reference(s): 22, 75 The unusual formation of planar trimethylenemethane (TMM) dianion complexes of lanthanide metallocenes, [(C5Me5)2Ln]2[m-h3:h3-C(CH2)3] (Ln = Sm, 1; La, 2; Pr, 3; Nd, 4; Y, 5) was examd.There are some reagents with their cas registry numbers 920533-28-4 and 5674-01-1 are used in this study. by synthesizing examples with metals from La to Y to examine the effects of radial size on structure and to provide closed shell examples for direct comparison with d. functional theory (DFT) calcns. Synthetic routes to 1-4 were expanded from the [(C5Me5)2Ln][(m-Ph)2BPh2]/neopentyl Li reaction involving b-Me elimination to a [(C5Me5)2Ln][(m-Ph)2BPh2]/isobutyl Li route. The synthetic pathways are sensitive to metal radius. To obtain 5, the methylallyl complex, (C5Me5)2Y[CH2C(Me)CH2], 6, was synthesized and treated with [(C5Me5)2YH]x. In the Lu case, the neopentyl complex [(C5Me5)2LuCH2CMe3]x, 7, was isolated instead of the TMM product. X-ray crystallog. showed that the metrical parameters of the planar TMM dianions in each complex are similar. The structural data were compared with DFT calcns. on the closed-shell La and Lu complexes that suggest only limited covalent interactions with the lanthanide ion. Benzophenone (2 equiv) reacts with 1 to expand the original four-C TMM skeleton to a dianionic bis(alkoxide) ligand contg. a sym. substituted C:CH2 moiety in [(C5Me5)2Sm]2[m-(OCPh2CH2)2C:CH2], 8. In this reaction, the TMM complex reacts as a bifunctional bisallylic reagent that generates an org. framework contg. a central vinyl group. .

Aldol-equivalent elaboration of sterically hindered ketiones: methallylmagnesium chloride as a synthon for acetone enolate

Aldol-equivalent elaboration of sterically hindered ketiones: methallylmagnesium chloride as a synthon for acetone enolate. Bunnelle, William H.; Rafferty, Moira A.; Hodges, Stephen L. (Dep. Chem., Univ. Missouri, Columbia, MO 65211, USA). J. Org. Chem., 52(8), 1603-5 (English) 1987. CODEN: JOCEAH. ISSN: 0022-3263. DOCUMENT TYPE: Journal CA Section: 23 (Aliphatic Compounds) The reaction of ketones with CH2:CMeCH2MgCl, followed by ozonolysis of the resulting homoallylic alcs., leads to b-ketols, which can be dehydrated to the corresponding enones. The entire procedure is formally equiv. to a crossed-aldol reaction with acetone enolate, and is particularly useful with hindered or easily enolized ketones, where traditional methods fail. The homologated ketol from (Me3C)2CO was resistant to dehydration, but its p-nitrobenzoate could be converted to the enone on treatment with base.Except for chemicals metioned above, 107036-01-1 and 5674-01-1 are also used. .