Development of Chiral Spiro P‐N‐S Ligands for Iridium‐Catalyzed Asymmetric Hydrogenation of β‐Alkyl‐β‐Ketoesters

Bao, Deng‐Hui; Wu, Huiling; Liu, Chaolun; Xie, Jian‐Hua; Zhou, Qi‐Lin

doi:10.1002/ange.201502860

Cited by 15 publications

(3 citation statements)

References 47 publications

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“…Our group has developed a number of highly effective catalytic asymmetric hydrogenation reactions. [15] [16] We wish to use Ir-catalyzed asymmetric hydrogenation of a β-keto ester [17] to construct a 1,3diol unit and Ir-catalyzed asymmetric hydrogenation of α-acrylic acid, [18] [19] to build the 1,3-methyl unit of deoxypropionates. By varying the configuration of catalysts, the absolute and relative configuration of newly formed stereogenic centers can be controlled.…”

Section: Resultsmentioning

confidence: 99%

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Enantioselective Total Synthesis of (−)‐Doliculide Using Catalytic Asymmetric Hydrogenations

Che

Wen

Zhu

et al. 2019

Helvetica Chimica Acta

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A concise and efficient strategy has been developed to construct a polyketide chain by employing relay asymmetric hydrogenations catalyzed by two chiral spiro iridium catalysts. By using this strategy, an enantioselective total synthesis of (−)‐doliculide has been achieved in 19 steps with 6.9 % overall yield. The route features high enantioselectivity and diastereoselectivity. The catalyst loading can be as low as 0.005 mol‐%. It is convenient to obtain natural polyketides and their analogues by this strategy.

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Section: Resultsmentioning

confidence: 99%

“…The diastereoisomeric ratio of product was determined after converting to amide with aniline. (4 (12 (13 (14 [(2R,3S,5S)-3-{[tert-Butyl(dimethyl)silyl]oxy}-5-(methoxymethoxy)-2,6-dimethylheptyl]-2,2-dimethyl-1,3-dioxane-4,6-dione (16 (17).…”

Section: General Procedures For Asymmetric Hydrogenations Of β-Keto Esmentioning

confidence: 99%

Enantioselective Total Synthesis of (−)‐Doliculide Using Catalytic Asymmetric Hydrogenations

Che

Wen

Zhu

et al. 2019

Helvetica Chimica Acta

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“…In 2011, Zhou et al demonstrated that the Ir/SpiroPAP catalyst may have a “metal-ligand bifunctional catalysis” mechanism similar to Noyori’s Ru/diphosphine/diamine system. Subsequently, iridium/SpiroPAP and iridium/SpiroPNS were applied to the asymmetric hydrogenation of β-keto esters by the same team, leading to excellent enantioselectivities (up to 99.9 and 95–99.9% ee, respectively) and an extremely high TON (1,230,000 and 355,000, respectively). Hu et al published an iridium catalyzed asymmetric hydrogenation of β - keto esters within chiral ferrocenyl P,N,N-ligands, providing good to excellent enantioselectivity.…”

Section: Introductionmentioning

confidence: 99%

Cinchona-Alkaloid-Derived NNP Ligand for Iridium-Catalyzed Asymmetric Hydrogenation of β-Keto Ester

Xu,

Gou,

Dai

et al. 2024

J. Org. Chem.

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The Ir-catalyzed asymmetric hydrogenation of βketo esters with Cinchona-alkaloid-derived NNP ligands has been developed. β-Hydroxy esters of opposite configuration were afforded smoothly with 91.5−99.1 and 81.6−99.3% ee, respectively, using NNP L2 and L7 derived from quinidine and quinine separately even on the gram scale. The protocol for the preparation of β-hydroxy esters of opposite configuration by the simple conversion of ligand configurations offered further opportunities for the synthesis of biologically active molecules and drugs.

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Iridium‐Catalyzed Enantioselective Hydrogenation of β,β‐Disubstituted Nitroalkenes

Liu

Kong

et al. 2015

Adv Synth Catal

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Ah ighly efficient, iridium-catalyzed, enantioselective hydrogenation of b,b-disubstituted nitroalkenesh as been developed. Using ac omplex consisting of iridium and (S,S)-f-spiroPhos as the catalyst, av ariety of b,b-disubstituted nitroalkenes were successfully hydrogenated to the corresponding chiral nitroalkanes with excellent enantioselectivities (up to 98% ee)a nd high turnover numbers (TON = 1000).Keywords: asymmetric catalysis; enantioselectivity; hydrogenation;i ridium;n itroalkenes Asymmetric hydrogenation represents one of the most economicala nd industrially revalvent synthetic methodsf or the production of enantiomerically pure chiral compounds. [1,2] Chiralf unctional groups can be transformed into various importantm oieties present in pharmaceuticals and biologically active molecules.[1] Thea symmetric hydogenation of b,b-disubstituted nitroalkenesr esults in chiral nitroalkanes, ac lass of important intermediates in the synthesiso f pharmacueticals.[3] It is wellk nown that nitro groups can be easily transformed into av ariety of functional groups including amines,a ldehydes,c arboxylica cids, nitrile oxides,a nd denitrated compounds.[4] These building blocks,s uch as chiral carboxylic acids and amines,a re present in manyd ifferent commercial pharmaceuticals including the well-known non-steroidal anti-inflammatory drug (NSAID), (+ +)-ibuprofen, [5] and the muscle relaxant, baclofen. [6] Due to the utility of chiral nitroalkanesi nc hemical synthesis, av ariety of synthetic methodst op roduce chiral nitroalkanes starting from nitroalkenes has been developed, such as asymmetric conjugate addition, [7] transfer hydrogenation, [8] biocatalysis.[9] However, the direct asymmetric hydrogenation of b,b-disubstituted nitroalkenesh as been relatively less explored. One recent example of ar hodium-catalyzed asymmetric hydrogenation of b,b-disubstituted nitroalkenes hasb een reported by Zhang et al, ande xcellent enantioselectivitiesw ere achieved. However, beside the high catalyst loading (e.g.,3mol% catalyst), it wass hown that the catalytic system wass ensitive to sterich indrance,a nd thus for substrates having as ubstituent in the ortho-position of the phenylr ing it resulted in poor to moderate conversion or enantioselectivity.[3] It hasb eens hownt hat iridium-based catalysts are more active to the asymmetric hydrogenation of certain classes of compoundsincluding unfunctionalized olefins, [2b,f] ketones, [10] unsaturated carboxylic acids [11] and imines. [12] We have also previously shown that the asymmetric hydrogenation of b-acylamino nitroolefins and a,b-unsaturated nitriles catalyzed by the Ir-o rR h-(S,S)-f-spiroPhos complexr esulted in enantioselectivitieso fu pt o9 8% ee and 99.9% ee,r espectively.[13] However, to the best of our knowledge,a ne fficient iridium catalyst for the asymmetrich ydrogenation of nitroalkenesw ithout any additional chelating groups has not yet been reported. When we evaluated the hydrogenation of b,b-disubstituted nitroalkenesw ith the Ir-(S,S)-f-spiroPhosc a...

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Development of Chiral Spiro P‐N‐S Ligands for Iridium‐Catalyzed Asymmetric Hydrogenation of β‐Alkyl‐β‐Ketoesters

Cited by 15 publications

References 47 publications

Enantioselective Total Synthesis of (−)‐Doliculide Using Catalytic Asymmetric Hydrogenations

Enantioselective Total Synthesis of (−)‐Doliculide Using Catalytic Asymmetric Hydrogenations

Cinchona-Alkaloid-Derived NNP Ligand for Iridium-Catalyzed Asymmetric Hydrogenation of β-Keto Ester

Iridium‐Catalyzed Enantioselective Hydrogenation of β,β‐Disubstituted Nitroalkenes

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