On the mechanism of catalytic enantioselective hetero-Diels–Alder reactions of carbonyl compounds catalyzed by chiral aluminum complexes—a concerted, step-wise or Mukaiyama–aldol pathway

Roberson, Mark; Jepsen, A.; Jørgensen, Karl Anker

doi:10.1016/s0040-4020(00)01046-2

Cited by 48 publications

(24 citation statements)

References 38 publications

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“…[20] The reaction was studied in the absence, and presence, of (MeO) 2 AlMe as a model catalyst for the BINOL ± AlMe system. The change in energy for the concerted HDA reaction, and formation of the HDA adduct by a Mukaiyama-aldol reaction, is shown in Figure 2.…”

Section: Chiral Aluminum and Boron Complexesmentioning

confidence: 99%

“…[50a] Cationic BINAP ± palladium and ±platinum complexes 35 a, b can catalyze highly enantioselective HDA reactions of arylglyoxals with acyclic and cyclic dienes [Eq. (20)]. [54] The HDA reaction proceeds well for reaction of phenylglyoxal 5 c with 2,3-dimethyl-1,3-butadiene (6 a) in the presence of the BINAP ligand and palladium(ii) and platinum(ii) salts giving 70 and 60 % yield, and 99 and 97 % ee, respectively, for the two Lewis acids.…”

Section: Chiral Transition Metal and Lanthanide Complexesmentioning

confidence: 99%

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Catalytic Asymmetric Hetero-Diels–Alder Reactions of Carbonyl Compounds and Imines

Jørgensen

2000

Angew. Chem. Int. Ed.

633

145

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Asymmetric catalysis is a challenge for chemists: How can we design catalysts to achieve the goal of forming optically active compounds? This review provides the reader with an overview of the development of catalytic asymmetric hetero‐Diels–Alder reactions of carbonyl compounds and imines. Since its discovery, the Diels–Alder reaction has undergone intensive development and is of fundamental importance for synthetic, physical, and theoretical chemists. The Diels–Alder reaction has been through different stages of development, and at the beginning of the 21st century catalytic Diels–Alder reactions are one of the main areas of focus. The preparation of numerous compounds of importance for our society is based on cycloaddition reactions to carbonyl compounds and imines. There are several parallels between the reactions of carbonyl compounds and those of imines, which, however, begin to vanish on entering the field of catalytic reactions. Why? From a mechanistic point of view some similarities can be drawn, but the synthetic development of catalytic enantioselective hetero‐Diels–Alder reactions of imines are several years behind those of the carbonyl compounds. For hetero‐Diels–Alder reactions of carbonyl compounds there a number of different chiral catalysts, and great progress has been achieved in developing enantioselective reactions for unactivated and activated carbonyl compounds. In contrast the development of catalytic enantioselective hetero‐Diels–Alder reactions of imines is in its infancy and only few catalytic reactions have been published. This review will focus on the most important developments, and discuss the synthetic and mechanistic aspects of enantioselective hetero‐Diels–Alder reactions of carbonyl compounds catalyzed by chiral Lewis acids. For the hetero‐Diels–Alder reactions of imines, the diastereoselective reactions of optically substrates catalyzed by Lewis acids will be presented first, followed by the catalytic enantioselective reactions.

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Section: Chiral Aluminum and Boron Complexesmentioning

confidence: 99%

Section: Chiral Transition Metal and Lanthanide Complexesmentioning

confidence: 99%

Catalytic Asymmetric Hetero-Diels–Alder Reactions of Carbonyl Compounds and Imines

Jørgensen

2000

Angew. Chem. Int. Ed.

633

145

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“…Herein we report further optimization of the HDA reaction catalyzed by dirhodium(II) carboxamidate catalysts 3 and 4 with aromatic aldehydes whose reactivity toward cycloaddition extends to nearly three orders of magnitude and, for the first time, kinetic analyses that add additional insight into the mechanism of this reaction. Although there have been theoretical investigations pertaining to the mechanism of the catalytic enantioselective HDA reaction (18,19) and extensive kinetic studies have been performed on the Diels-Alder reaction (20)(21)(22)(23), to our knowledge, detailed kinetic studies have not been performed on the HDA reaction (24,25). The dirhodium(II) catalytic system provides unique opportunities for these evaluations because they are amenable to determination of equilibrium constants for association between catalyst and aldehyde and to the monitoring of rates for reaction.…”

mentioning

confidence: 99%

Asymmetric hetero-Diels–Alder reaction catalyzed by dirhodium(II) carboxamidates

Doyle

Valenzuela

Huang

2004

Proc. Natl. Acad. Sci. U.S.A.

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Chiral dirhodium(II) carboxamidates are highly efficient catalysts for reactions between a variety of aldehydes and activated dienes. Catalyst loadings as low at 0.01 mol % have been realized with enantioselectivities up to 97%. Kinetic investigations reveal a pronounced electronic influence on the rate of the hetero-DielsAlder reaction with a Hammett value of ؉1.9 (versus ؉ ). Inhibition of the catalyst by reactant aldehyde is apparent, but reactions show first-order dependence on aldehyde and diene, and there is a variable dependence on catalyst.

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“…In terms of ligand, the Jørgensen group [15] employed the chiral 1,1Ј-binaphthol (BINOL) ligand and the Yamada group [19] adopted the salen ligand. They also performed theoretical studies on HDA reactions catalyzed by metal (aluminum and cobalt, respectively) complexes.…”

Section: Addition Of Butadiene To Com-a and Com-bmentioning

confidence: 99%

“…When Lewis acid BH 3 (the catalyst) coordinated to the oxygen atom of formaldehyde, the activation energy of the reaction decreased drastically and the asynchronicity increased in the transition structure. Later, the Jørgensen group [15] studied the reaction of benzaldehyde with Danishefsky's diene catalyzed by various aluminum complexes by using AM1 and ab initio methods. Their results indicated that the concerted reaction occurred most likely through the Diels-Alder cycloaddition mechanism without any catalysts, although Mukaiyama aldol pathways were found when the reactions were catalyzed by (MeO) 2 AlMe and (S)-BINOL/AlMe.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study on Hetero‐Diels–Alder Reaction of Butadiene with Benzaldehyde Catalyzed by Chiral In^III Complexes

Cao

Qin

et al. 2010

Eur J Org Chem

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The mechanism of the hetero-Diels-Alder reaction of butadiene with benzaldehyde catalyzed by chiral N,NЈ-dioxide/ In(OTf) 3 complexes was studied theoretically by using density functional theory (DFT) and model system. The computational results indicate that the catalyzed reaction proceeded through a concerted mechanism via a highly zwitterionic transition state. The lowest energy barrier was 11.8 kJ mol -1 , which is 63.0 kJ mol -1 lower than that of the uncatalyzed reaction. The results indicate that the endo approach is advantageous over the exo approach, because exo transitions states suffer from more steric hindrance than the endo transitions states as a result of interactions among the substrates,

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On the mechanism of catalytic enantioselective hetero-Diels–Alder reactions of carbonyl compounds catalyzed by chiral aluminum complexes—a concerted, step-wise or Mukaiyama–aldol pathway

Cited by 48 publications

References 38 publications

Catalytic Asymmetric Hetero-Diels–Alder Reactions of Carbonyl Compounds and Imines

Catalytic Asymmetric Hetero-Diels–Alder Reactions of Carbonyl Compounds and Imines

Asymmetric hetero-Diels–Alder reaction catalyzed by dirhodium(II) carboxamidates

Theoretical Study on Hetero‐Diels–Alder Reaction of Butadiene with Benzaldehyde Catalyzed by Chiral In^III Complexes

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On the mechanism of catalytic enantioselective hetero-Diels–Alder reactions of carbonyl compounds catalyzed by chiral aluminum complexes—a concerted, step-wise or Mukaiyama–aldol pathway

Cited by 48 publications

References 38 publications

Catalytic Asymmetric Hetero-Diels–Alder Reactions of Carbonyl Compounds and Imines

Catalytic Asymmetric Hetero-Diels–Alder Reactions of Carbonyl Compounds and Imines

Asymmetric hetero-Diels–Alder reaction catalyzed by dirhodium(II) carboxamidates

Theoretical Study on Hetero‐Diels–Alder Reaction of Butadiene with Benzaldehyde Catalyzed by Chiral InIII Complexes

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Theoretical Study on Hetero‐Diels–Alder Reaction of Butadiene with Benzaldehyde Catalyzed by Chiral In^III Complexes