Asymmetric cyclization reactions. Cyclization of substituted 4-pentenals into cyclopentanone derivatives by rhodium(I) with chiral ligands

Taura, Y.; Tanaka, Masakazu; Wu, Xueyuan; Funakoshi, Kazuhisa; Saito, Kiyoshi

doi:10.1016/s0040-4020(01)80954-6

Cited by 67 publications

(19 citation statements)

References 20 publications

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“…4- n- Butylpenten-1-al ( 299a , where R = n Bu) was treated with the neutral chlorobis(cyclooctene)Rh(I) dimer and chiral bisphosphine ligand (+)-DIPMC, resulting in an intramolecular cyclization to provide the corresponding cyclopentanone derivative 300a in 78% yield and 73% ee. In 1991, Sakai and co-workers demonstrated that these same conditions were suitable for the analogous phenyl- and tert -butyl-substituted derivatives, with similar selectivities observed for all three substrates . Despite the near-stoichiometric catalyst loading (50 mol % of Rh), this landmark study demonstrated that the hydroacylation reaction of achiral aldehydes could be rendered enantioselective.…”

Section: Stereochemistry-generating Migratory Insertionmentioning

confidence: 99%

Catalytic Enantioselective Transformations Involving C–H Bond Cleavage by Transition-Metal Complexes

et al. 2017

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The development of new methods for the direct functionalization of unactivated C-H bonds is ushering in a paradigm shift in the field of retrosynthetic analysis. In particular, the catalytic enantioselective functionalization of C-H bonds represents a highly atom- and step-economic approach toward the generation of structural complexity. However, as a result of their ubiquity and low reactivity, controlling both the chemo- and stereoselectivity of such processes constitutes a significant challenge. Herein we comprehensively review all asymmetric transition-metal-catalyzed methodologies that are believed to proceed via an inner-sphere-type mechanism, with an emphasis on the nature of stereochemistry generation. Our analysis serves to document the considerable and rapid progress within in the field, while also highlighting limitations of current methods.

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Section: Stereochemistry-generating Migratory Insertionmentioning

confidence: 99%

Catalytic Enantioselective Transformations Involving C–H Bond Cleavage by Transition-Metal Complexes

et al. 2017

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“…Finally, 4-substituted 4-penten-1-ols 53 [46] and 54 were treated with TBHP and catalyst 4g (Scheme 5). Oxidation of prostereogenic substrate 53 under such conditions furnished 82% of racemic 2-(hydroxymethyl)-2-phenyltetrahydrofuran (55).…”

Section: Vanadium(v)-catalyzed Oxidations Of Bis(homoallylic) Alcoholsmentioning

confidence: 99%

(Schiff‐base)vanadium(V) Complex‐Catalyzed Oxidations of Substituted Bis(homoallylic) Alcohols − Stereoselective Synthesis of Functionalized Tetrahydrofurans

et al. 2003

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Keywords: Oxidation / Tetrahydrofuran / Catalysis / Asymmetric synthesis / Vanadium Vanadium(V) complexes 4 have been prepared from tridentate Schiff-base ligands 3 and VO(OEt) 3 . All vanadium(V) compounds were characterized (IR, UV/Vis, and 51 V NMR spectroscopy, and in selected examples by X-ray diffraction analysis) and were applied as oxidation catalysts for the stereoselective synthesis of functionalized tetrahydrofurans 2 starting from substituted bis(homoallylic) alcohols 1 (mono-or trisubstituted C−C double bonds). Oxidation of secondary or tertiary 1-alkyl-, 1-vinyl-, or 1-phenyl-substituted 5,5-dimethyl-4-penten-1-ols under optimized conditions [TBHP as primary oxidant and 1,2-(amino)indanol-derived vanadium(V) reagent 4g as catalyst] provided 2,5-cis-configured tetrahydrofurans in synthetically useful yields and diastereoselectivities (22−96% de). On the other hand, trans-disubstituted oxolanes (62%−96 de) were obtained from oxidations of 2-or 3-alkyl-and 2-or 3-phenyl-substituted 5,5-dimethyl-4-penten-1-ols bis(homoallylic) alcohols. Treatment of 4-penten-1-ols (i.e. substrates with monosubstituted olefinic π-bonds) with TBHP and catalytic amounts of vanadium(V) complex 4g furnished trans-disubstituted tetrahydrofurans as major products (20−96% de), no matter whether an alkyl or a phenyl substituent was located in position 1, 2, or 3 of the alkenol chain. The mechanism of this reaction has been investigated in detail. Based on re-

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“…2) After that, this hydroacylation of 4-alkenals has been expanded to a catalytic process 3,4) and asymmetric reaction. [5][6][7][8][9][10][11][12][13][14][15][16][17][18] The proposed reaction mechanism is shown in Chart 1. Initially, oxidative addition of the C-H bond of the aldehyde moiety to the rhodium complex occurs to form acylrhodium intermediate i followed by insertion of an alkene moiety to the Rh-H bond to give the 6-membered rhodacycle intermediate ii.…”

Section: Introductionmentioning

confidence: 99%

Development of Novel Cyclizations <i>via</i> Rhodacycle Intermediate and Its Application to Synthetic Organic Chemistry

Oonishi

2015

Chem. Pharm. Bull.

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Novel Rh(I)-catalyzed cyclizations through a different type of rhodacycle intermediate which is formedby hydroacylation of 4,6-dienal or oxidative addition of diene and alkene are described. Hydroacylation of 4,6-dienal afforded various 7-membered rings in good to high yields, while cycloisomerization of diene and alkene provided 5-or 6-membered rings in good yields. On the basis of these studies, we have also succeeded in developing the sequential reaction of hydroacylation followed by cycloisomerization to produce bicyclic compounds in a stereoselective manner and thus this reaction was expanded to the synthesis of epiglobulol. Furthermore, both Rh(I)-catalyzed hydroacylation and cycloisomerization using ionic liquid (IL) as a solvent were investigated and it was found that the IL recovered after the reaction, which contains the Rh(I) catalyst, could be recycled several times without loss of catalytic activity.

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Asymmetric cyclization reactions. Cyclization of substituted 4-pentenals into cyclopentanone derivatives by rhodium(I) with chiral ligands

Cited by 67 publications

References 20 publications

Catalytic Enantioselective Transformations Involving C–H Bond Cleavage by Transition-Metal Complexes

Catalytic Enantioselective Transformations Involving C–H Bond Cleavage by Transition-Metal Complexes

(Schiff‐base)vanadium(V) Complex‐Catalyzed Oxidations of Substituted Bis(homoallylic) Alcohols − Stereoselective Synthesis of Functionalized Tetrahydrofurans

Development of Novel Cyclizations <i>via</i> Rhodacycle Intermediate and Its Application to Synthetic Organic Chemistry

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