Asymmetric ene reactions in organic synthesis

Mikami, Kōichi; Shimizu, Masaki

doi:10.1021/cr00013a014

Cited by 613 publications

(188 citation statements)

References 46 publications

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“…It is commonly accepted that the cyclization of citronellal occurs through a concerted mechanism [44,[78][79][80] More details regarding the reaction mechanism of a standard carbonyl-ene reaction [81] are given in Section 1 of the Supplementary Material (SI). Citronellal cyclization has also been investigated on solid Lewis acid catalysts.…”

Section: Mechanism Of the Citronellal Cyclization On Lewis Acid Catalmentioning

confidence: 99%

Insight in the activity and diastereoselectivity of various Lewis acid catalysts for the citronellal cyclization

Vandichel

Vermoortele

Cottenie

et al. 2013

Journal of Catalysis

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RECEIVED DATE (to be automatically inserted after your manuscript is accepted if required according to the journal that you are submitting your paper to) TITLE RUNNING HEAD Kinetics of the Lewis acid catalyzed citronellal cyclization 2 ABSTRACT Industrial (-)-menthol production generally relies on the hydrogenation of (-)-isopulegol, which is in turn produced with high selectivity by cyclization of (+)-citronellal. This paper uses a combined theoretical and experimental approach to study the activity and selectivity of three Lewis acid catalysts for this reaction, namely ZnBr 2 , aluminum tris(2,6-diphenylphenoxide) (ATPH) and the heterogeneous metal-organic framework Cu 3 BTC 2 (BTC = benzene-1,3,5-tricarboxylate). ATPH is a strong Lewis acid homogeneous catalyst with bulky ligands which provides very high selectivities for the desired stereoisomer (> 99 %). The performance of the catalysts was evaluated as a function of temperature, which revealed that higher catalyst activity allows working at lower temperatures and improves the selectivity for isopulegol. The selectivity distribution is kinetically driven for ZnBr 2 and ATPH. The theoretical selectivity distributions rely on the determination of an extensive set of diastereomeric transition states, for which the differences in free energy have been calculated using a complementary set of ab initio techniques. Given the sensitivity of the selectivity to small Gibbs free energy differences, the agreement between experimental and theoretical selectivities is satisfactory. On basis of the obtained insights rational design of new catalysts may be obtained. As proof of concept, the hypothetical Cu 3 (BTC-(NO 2 ) 3 ) 2 Lewis catalyst -in which each phenyl hydrogen of the BTC ligand is replaced by a nitro group -is predicted to be very selective.

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Section: Mechanism Of the Citronellal Cyclization On Lewis Acid Catalmentioning

confidence: 99%

Insight in the activity and diastereoselectivity of various Lewis acid catalysts for the citronellal cyclization

Vandichel

Vermoortele

Cottenie

et al. 2013

Journal of Catalysis

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“…Various substituents at the aromatic ring lead to multiple chemical modifications which generates antioxidant, anti-inflammatory, antibacterial and anticancer activities for these compounds [6]. Recognizing the considerable importance of the compounds, research focused on the synthesis of enone derivatives.…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of 4a-Hydroxy-9-(2-nitro-phenyl)-3,4,4a,5,6,7,9,9a-octahydro-2H-xanthene-1,8-dione, C₁₉H₁₉NO₆

2017

Zeitschrift Für Kristallographie - New Crystal Structures

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“…烯(ene)反应是有机合成中一类简单实用的化学反应, 根据亲电试剂的不同可合成官能团多样化的产物 [25] . 从反应的过渡态考虑, 烯反应也被认为是一类 π 2s ＋π 2s ＋σ 2s 反应 [26] (Scheme 6).…”

Section: 亚硝基-烯反应的介绍unclassified

Research Progress on Nitroso-ene Reaction

黄莎华¹,

霍华兴²,

李文华³

et al. 2012

Chin. J. Org. Chem.

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Asymmetric ene reactions in organic synthesis

Cited by 613 publications

References 46 publications

Insight in the activity and diastereoselectivity of various Lewis acid catalysts for the citronellal cyclization

Insight in the activity and diastereoselectivity of various Lewis acid catalysts for the citronellal cyclization

Crystal structure of 4a-Hydroxy-9-(2-nitro-phenyl)-3,4,4a,5,6,7,9,9a-octahydro-2H-xanthene-1,8-dione, C₁₉H₁₉NO₆

Research Progress on Nitroso-ene Reaction

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Asymmetric ene reactions in organic synthesis

Cited by 613 publications

References 46 publications

Insight in the activity and diastereoselectivity of various Lewis acid catalysts for the citronellal cyclization

Insight in the activity and diastereoselectivity of various Lewis acid catalysts for the citronellal cyclization

Crystal structure of 4a-Hydroxy-9-(2-nitro-phenyl)-3,4,4a,5,6,7,9,9a-octahydro-2H-xanthene-1,8-dione, C19H19NO6

Research Progress on Nitroso-ene Reaction

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Crystal structure of 4a-Hydroxy-9-(2-nitro-phenyl)-3,4,4a,5,6,7,9,9a-octahydro-2H-xanthene-1,8-dione, C₁₉H₁₉NO₆