Asymmetric hetero-Diels-Alder reaction catalyzed by a chiral organoaluminum reagent

Maruoka, Keiji; Itoh, Takayuki; Shirasaka, Tadashi; Yamamoto, Hisashi

doi:10.1021/ja00209a061

Cited by 283 publications

(71 citation statements)

References 2 publications

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“…An asymmetric hetero-Diels Alder reaction was recently reported using a C 2 -symmetric BINOL catalyst (Scheme 60). 77 Chiral aluminium complex 264 has been shown to impart good enantioselectivity in these syntheses of dihydropyrones (97% ee) as well as in ene reactions (up to 88% ee) and asymmetric Claisen rearrangements (up to 93% ee). Extension of our ortho-functionalized hydrobenzoin derivatives to this reaction may provide a more selective and economical route to this class of molecules.…”

Section: Resultsmentioning

confidence: 99%

Bidirectional Metalation of Hydrobenzoin: Direct Access to New Chiral Ligands and Auxiliaries

2009

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Section: Resultsmentioning

confidence: 99%

Bidirectional Metalation of Hydrobenzoin: Direct Access to New Chiral Ligands and Auxiliaries

2009

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“…Finally, Yamamoto et al reported the reaction to proceed in 56 % ee in the presence of a highly sterically hindered substituted BINOL-AlMe 3 derived catalyst, but no yield was given, and the intermediate of the reaction was not determined. [9] There appears to be a firm correlation between the pathway and the Lewis acid employed. The Mukaiyama pathway has so far only been observed with catalysts based on titanium [6] and boron [5] complexes, while the Diels ± Alder pathway has been positively identified in reactions catalyzed by Lewis acids based on europium, [7] chromium, [8] and zinc.…”

Section: Diels-alder Pathmentioning

confidence: 99%

Development of an Unusually Highly Enantioselective Hetero-Diels-Alder Reaction of Benzaldehyde with Activated Dienes Catalyzed by Hypercoordinating Chiral Aluminum Complexes

et al. 2000

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The effect of Lewis acid catalysis of the hetero-Diels-Alder reaction between benzaldehyde and activated dienes (e.g. the Danishefsky's diene) has been investigated. In the present work we decided to study a series of chiral aluminum complexes as potential catalysts for the hetero-Diels-Alder reaction in order to gain a better understanding of the effect on the chiral induction of varying the steric and electronic environment of the metal ion. The results of this study prompted us to conclude that steric effects in the ligand coordination sphere and hypercoordination are strongly contributing factors to the optical yield of the reaction. Optimization of the reaction culminated in the synthesis of the hetero-Diels-Alder product in 99.4% ee and 97% yield of the isolated product. Based on the experimental results the mechanism for the hetero-Diels-Alder reaction is discussed and it is postulated that hypercoordination to the chiral aluminum Lewis acid center is of importance for the reaction.

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“…9) [50]. Since then, a lot of catalytic asymmetric reactions utilizing this type of mononucleus aluminum catalysts have been developed [6].…”

Section: Binol-aluminum Complex Based Catalystsmentioning

confidence: 99%

Bifunctional Acid Catalysts for Organic Synthesis

Yamamoto

2011

Bifunctional Molecular Catalysis

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The concept of bifunctional acid catalysis is very helpful for inventing new catalytic asymmetric reactions. Compared with single functional acid catalysts, cooperative effect of two acid components has the potential to fine tune the reactivity as well as the selectivity of desired reaction pathways. This chapter focuses on some representative examples on the recent developments of bifunctional acid catalysis, including combined acid catalysis and other cooperative acid catalysis.

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Asymmetric hetero-Diels-Alder reaction catalyzed by a chiral organoaluminum reagent

Cited by 283 publications

References 2 publications

Bidirectional Metalation of Hydrobenzoin: Direct Access to New Chiral Ligands and Auxiliaries

Bidirectional Metalation of Hydrobenzoin: Direct Access to New Chiral Ligands and Auxiliaries

Development of an Unusually Highly Enantioselective Hetero-Diels-Alder Reaction of Benzaldehyde with Activated Dienes Catalyzed by Hypercoordinating Chiral Aluminum Complexes

Bifunctional Acid Catalysts for Organic Synthesis

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