Asymmetric γ‐Allylation of α,β‐Unsaturated Aldehydes by Combined Organocatalysis and Transition‐Metal Catalysis

Næsborg, Line; Halskov, Kim Søholm; Tur, Fernando; Mønsted, Sofie M. N.; Jørgensen, Karl Anker

doi:10.1002/anie.201504749

Cited by 161 publications

(79 citation statements)

References 56 publications

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“…[268] This approach rests on the ability of ac hiral Ir-complex and ab enzotetramisole catalyst to independently set two stereocenters.Inaddition to these approaches,anumber of elegant dual catalytic systems have been developed recently,demonstrating the increasing interest in stereodivergent catalytic methods. [269] Adifferent cascade catalytic system was developed by the group of MacMillan. Theiminium formed upon condensation of enal 256 with the catalyst (259)i sa ttacked by furan 257.…”

Section: Angewandte Chemiementioning

confidence: 99%

Enantioselective Chemo‐ and Biocatalysis: Partners in Retrosynthesis

et al. 2017

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Recent developments of stereoselective biocatalytic and chemocatalytic methods are discussed. The review provides a guide to the use of biocatalytic methods in the area of chemical synthesis with focused attention on retrosynthetic considerations and analysis. The transformations presented are organized according to bond disconnections and attendant synthetic methods. The review is expected to lead to better understanding of the characteristics and distinctions of the two complementary approaches. It depicts for researchers in bio- and chemocatalysis a road map of challenges and opportunities for the evolution (and at times revolution) in chemical synthesis.

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Section: Angewandte Chemiementioning

confidence: 99%

Enantioselective Chemo‐ and Biocatalysis: Partners in Retrosynthesis

et al. 2017

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“…[2,3] The field of asymmetric synthesis deals with these situations, often masterfully, through the application of chiral catalysts, [3] which can take the form of transition metal complexes, [4] small organic molecules, [5] enzymes, [6] or combinations of a metal-based catalyst and an organocatalyst. [7] A particularly intriguing situation emerges when the scaffold of interest bears two different types of stereogenic elements. [8] For example, when a molecule possesses both a stereogenic center (Figure 1a), and an axis of chirality (Figure 1b), four possible diastereomers exist (Figure 1c) in a manner rendering asymmetric synthesis of all possible stereoisomers quite complex.…”

mentioning

confidence: 99%

Divergent Control of Point and Axial Stereogenicity: Catalytic Enantioselective C−N Bond‐Forming Cross‐Coupling and Catalyst‐Controlled Atroposelective Cyclodehydration

et al. 2018

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Catalyst control over reactions that produce multiple stereoisomers is a challenge in synthesis. Control over reactions that involve stereogenic elements remote from one another is particularly uncommon. Additionally, catalytic reactions that address both stereogenic carbon centers and an element of axial chirality are also rare. Reported herein is a catalytic approach to each stereoisomer of a scaffold containing a stereogenic center remote from an axis of chirality. Newly developed peptidyl copper complexes catalyze an unprecedented remote desymmetrization involving enantioselective C-N bond-forming cross-coupling. Then, chiral phosphoric acid catalysts set an axis of chirality through an unprecedented atroposelective cyclodehydration to form a heterocycle with high diastereoselectivity. The application of chiral copper complexes and phosphoric acids provides access to each stereoisomer of a framework with two different elements of stereogenicity.

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“…As a powerful strategy for addressing this intrinsic problem, catalyst-directed diastereodivergence would be much sought after. Impressive progress has been made in the development of diastereodivergent asymmetric catalysis for carbon–carbon and carbon-heteroatom bond-forming reactions234567891011121314151617181920212223242526272829303132. However, most of the processes currently available rely on using each elaborated catalyst, or the appropriate combination of two different catalysts, to access complementary diastereomers selectively.…”

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confidence: 99%

Complete diastereodivergence in asymmetric 1,6-addition reactions enabled by minimal modification of a chiral catalyst

Uraguchi¹,

Yoshioka²,

Ooi³

2017

Nat Commun

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Catalytic systems that allow selective generation of any diastereomer of a reaction product bearing multiple stereocentres through minimal modification of a single catalyst scaffold remain elusive, particularly for carbon–carbon bond formations requiring simultaneous control of multiple selectivity factors. Here, we report a catalyst-directed pinpoint inversion of diastereochemical preference in the 1,6-addition of azlactones to δ-aryl dienyl carbonyl compounds with full control over other selectivities preserved. This rigorous diastereodivergence is enabled by the slight structural adjustment of a chiral iminophosphorane catalyst, providing access to all the stereoisomers with high regio-, distereo- and enantioselectivity. The utility of this method is demonstrated in the facile stereodivergent preparation of densely functionalized proline derivatives. The experimental and computational elucidation of the origin of the diastereodivergence is also reported.

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Asymmetric γ‐Allylation of α,β‐Unsaturated Aldehydes by Combined Organocatalysis and Transition‐Metal Catalysis

Cited by 161 publications

References 56 publications

Enantioselective Chemo‐ and Biocatalysis: Partners in Retrosynthesis

Enantioselective Chemo‐ and Biocatalysis: Partners in Retrosynthesis

Divergent Control of Point and Axial Stereogenicity: Catalytic Enantioselective C−N Bond‐Forming Cross‐Coupling and Catalyst‐Controlled Atroposelective Cyclodehydration

Complete diastereodivergence in asymmetric 1,6-addition reactions enabled by minimal modification of a chiral catalyst

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