Recent Developments in Enantioselective Multicatalyzed Tandem Reactions

Pellissier, Hélène

doi:10.1002/adsc.202000210

Cited by 44 publications

(26 citation statements)

References 253 publications

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“…15 The issues are further enhanced in asymmetric catalysis, where any cross-reactivity is likely to deteriorate the stereoselectivity of the intended transformations. [34][35][36][37][38][39] Stereoselective synthesis has been facilitated by the development of transition metal-catalyzed asymmetric hydrogenation. [40][41][42] For instance, secondary benzylic alcohols, a prevalent moiety in biologically active molecules and valuable building blocks in synthesis, [43][44][45][46][47] are readily prepared by enantioselective hydrogenation of aryl ketones in the presence of chiral Ru-complexes developed by Noyori.…”

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confidence: 99%

Multicatalytic Approach to One-Pot Stereoselective Synthesis of Secondary Benzylic Alcohols

et al. 2021

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One-pot multi-step procedures bear the potential to rapidly build up molecular complexity while avoiding the wasteful and costly isolations and purifications of consecutive intermediates. Here we report multi-catalytic protocols that convert alkenes, unsaturated aliphatic alcohols, and aryl boronic acids into secondary benzylic alcohols with high stereoselectivities under sequential catalysis that integrates alkene cross-metathesis, isomerization, and nucleophilic addition. Because each transformation of the sequence is executed by an independent catalyst, without any catalytic cross-reactivity, allylic alcohols bearing a prochiral double bond can be converted to any stereoisomer of the product with high stereoselectivity (>98:2 er and >20:1 dr). Overall, with the aid of up to four catalysts operating in a single vessel, the protocols directly convert simple starting materials into a range of value-added products with high stereocontrol and excellent material efficiency, demonstrating both the efficacy and the advantages of the one-pot synthesis employing multiple transition-metal catalysts.

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confidence: 99%

Multicatalytic Approach to One-Pot Stereoselective Synthesis of Secondary Benzylic Alcohols

et al. 2021

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“…[21][22][23][24][25] Special attention must be paid to the selection of the catalysts, considering that any cross-reactivity or any ligand scrambling is likely not only to decrease the required activity but also be detrimental for the overall stereoselectivity. 26,27 The Ru-catalyst containing me-bipam, a chiral phosphoramidite ligand developed by Yamamoto and Miyaura, proved previously both highly enantioselective in the arylation of aldehydes 28,29 and compatible with a series of phosphine-Ru complexes, 18 which represent prospective hydrogen-transfer catalysts. 19,20 Therefore, Ru-complex bearing me-bipam was selected as a catalyst of choice for the 1,2-addition step, and the main efforts for the method development were focused on identifying a phosphine-Ru-based hydrogen-transfer catalyst and a sacrificial hydrogen acceptor (HA).…”

Section: Scheme 1 Synthesis Of Secondary Benzylic Alcohols From Simple Alcohols -Context Of This Workmentioning

confidence: 99%

Enantioselective α-Arylation of Primary Alcohols under Sequential One-Pot Catalysis

et al. 2021

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Secondary benzylic alcohols (SBAs) and diarylmethanols (DAMs) are common structural motifs of biologically active and medicinally relevant compounds. Here we report their enantioselective synthesis by -arylation of primary aliphatic and benzylic alcohols under sequential catalysis integrating a Ru-catalyzed hydrogen-transfer oxidation and a Ru-catalyzed nucleophilic addition. The method is applicable to various alcohols and aryl nucleophiles tolerating a range of functional groups, including secondary alcohols, ketones, alkenes, esters, NH-amides, tertiary amines, aryl halides, and heterocycles.Secondary benzylic alcohols (SBAs) and diarylmethanols (DA Ms) constitute valuable synthetic intermediates and prevalent structural motifs of numerous natural products and bioactive compounds. 1,2 Therefore, protocols for their stereoselective synthesis from various accessible starting materials have attracted much attention over the years. Common approaches include potent asymmetric (transfer) hydrogenation of ketones 1,3,4 or 1,2-addition of aryl nucleophiles to aldehydes, 5,6 particularly useful for fine-chemical synthesis when such starting materials are available and do not require additional synthetic steps.Because aliphatic alcohols represent a class of abundant starting materials, increasing attention has been devoted to developing methods for their valorization through selective C−H bond functionalization. [7][8][9] In the context of SBAs, an elegant strategy for the enantioselective alkylation of -C−H bonds of primary benzylic alcohols with unsaturated hydrocarbons (e.g., dienes, enynes) was devised by Krische and co-workers (Scheme 1a). 10,11 The methods of the arylation of -C−H bonds of aliphatic alcohols in the Minisci-type reactions were also established. [12][13][14][15][16][17] (Scheme 1b). Unfortunately, these methods lead to racemic products, leaving the enantioselective -C−H arylation of alcohols unexplored.We have recently reported an enantioselective synthesis of SBAs from unsaturated alcohols and aryl boronic acids under sequential catalysis (Scheme 1c). 18 The one-pot sequence of an Ir-catalyzed isomerization of the starting material and a Ru-catalyzed nucleophilic addition of an aryl boronic acid to the aldehyde intermediate provided a convenient synthetic method with a broad scope and functional group tolerance.

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“…However, the field continues evolving in complexity to further increase its potential. [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] Recently, there has been growing interest in developing multi-catalytic systems, which are inspired by the complexity of catalytic reactions occurring in nature. 20,21 Such efforts are further driven by remarkable characteristics of biosynthesis, that is, excellent selectivity, high yields, and material efficiency when producing complex molecules directly without any isolation of intermediates.…”

Section: Introductionmentioning

confidence: 99%

Challenges and Opportunities in Multicatalysis

et al. 2021

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Multi-catalysis is an emerging field targeting the development of efficient catalytic transformations to quickly convert relatively simple starting materials into more complex valueadded products. Within multi-catalytic processes either multiple catalysts execute single reactions or precise sequences of multiple catalytic reactions occur in a 'one-pot' fashion. Attractively, multi-catalytic protocols not only enable transformations that are inaccessible through classic approaches, but also are able to significantly reduce the time, waste, and cost of the synthetic processes, making organic synthesis more resources efficient. In this Perspective article, we review different strategies in multi-catalysis that bring distinct challenges and opportunities. We divide this overarching field into three main categories: cooperative, domino, and relay catalysis. Each category is described along with representative examples to highlight its features. Special emphasis is dedicated to relay catalysis, which is further discussed in its sub-categories. Lastly, we provide an analysis of systems that incorporate higher levels of complexity and further underscore the potential of multi-catalytic systems.

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Recent Developments in Enantioselective Multicatalyzed Tandem Reactions

Cited by 44 publications

References 253 publications

Multicatalytic Approach to One-Pot Stereoselective Synthesis of Secondary Benzylic Alcohols

Multicatalytic Approach to One-Pot Stereoselective Synthesis of Secondary Benzylic Alcohols

Enantioselective α-Arylation of Primary Alcohols under Sequential One-Pot Catalysis

Challenges and Opportunities in Multicatalysis

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