Lipase-catalyzed domino Michael–aldol reaction of 2-methyl-1,3-cycloalkanedione and methyl vinyl ketone for the synthesis of bicyclic compounds

Sano, Kaoru; Kohari, Yoshihito; Nakano, Hiroto; Seki, Chigusa; Takeshita, Mitsuhiro; Tokiwa, Michio; Hirose, Yoshio; Uwai, Koji

doi:10.1080/00397911.2015.1116584

Cited by 13 publications

(5 citation statements)

References 27 publications

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“…Uwai et al. in 2016 performed the synthesis of bicyclic compounds using 1,3‐diketones and methyl vinyl ketone as substrates in the lipase catalyzed domino Michael‐aldol reaction ( Scheme ) . Various lipases were screened for the synthesis of Wieland–Miescher ketone.…”

Section: Introductionmentioning

confidence: 99%

Promiscuity of Lipase‐Catalyzed Reactions for Organic Synthesis: A Recent Update

et al. 2018

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Lipase-catalyzed organic reactions have widely been practiced in the past three decades. In addition to its wide acceptance in conventional reactions such as hydrolysis, transesterification, and enantiopure synthesis (kinetic resolution and dynamic kinetic resolution) several reports on the catalytic promiscuity of lipases have also been published. The concept of promiscuity, where lipase catalyzes reactions beyond its natural function, has been perceived as a useful phenomenon which can enhance the utility of lipase as a biocatalyst. Many useful organic reactions such as Aldol condensation, Hantzsch reaction, Canizzaro reaction, Mannich reaction, Baylis-Hillman reaction, Knoevenagel condensation, Michael addition, Ugi reaction, and oxidation catalyzed by lipases have surfaced in the literature. The current review is a critical compilation of such research findings to put forth the synthetic applications of lipase, beyond the orthodox biocatalytic toolbox.

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Section: Introductionmentioning

confidence: 99%

Promiscuity of Lipase‐Catalyzed Reactions for Organic Synthesis: A Recent Update

et al. 2018

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“…It should be noted that previous attempts at accessing enantioenriched 22n using organocatalysis were unsuccessful . The synthesis of this compound has been reported very recently using lipases as a biocatalyst; however, very poor values of enantiomeric excess (8% ee) were achieved and extremely prolonged reaction times (8 days) were needed . In our case, the seven-membered-ring bicyclic enone 22n was obtained in good yield (77%) and moderate enantiomeric excess (53%) in a rather short reaction time (12 h).…”

Section: Resultsmentioning

confidence: 61%

A Highly Active Polymer-Supported Catalyst for Asymmetric Robinson Annulations in Continuous Flow

et al. 2017

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ABSTRACT:The preparation through Robinson annulation of enantiopure building blocks with both academic and industrial relevance, such as the Wieland-Miescher and Hajos-Parrish ketones, has suffered from important drawbacks, such as the need of high catalyst loading or extremely long reaction times. Here we report a heterogeneized organocatalyst based on Luo's diamine for the fast and broad-scope enantioselective Robinson annulation reaction. The polystyrene-supported diamine 19a enables the high-yield, highly enantioselective preparation of a wide scope of chiral bicyclic enones under mild conditions, with reaction times as short as 60 minutes (batch) or residence times of 10 minutes (flow). In contrast with its homogeneous counterpart 19b, the catalytic resin 19a experiences a notable increase in catalytic activity with temperature in 2-MeTHF (a ten-fold decrease in reaction times without erosion in enantioselectivity is observed from room temperature to 55 ºC). The scope of the transformation in batch has been illustrated with 14 examples, including examples only reported in poorly enantioenriched (22n) or in racemic form (22k). Enantiopure 22k has been used as starting material for a straightforward formal synthesis of the antibiotic and antifeedant sesquiterpene (−)-isovelleral (24). The heterogeneized catalyst 19a admits extended recycling (10 cycles) and has been used to develop the first asymmetric Robinson annulations in continuous flow. The potential of the flow process is illustrated by the large scale preparation of the Wieland-Miescher ketone (65 mmol in 24 h operation, TON of 117) and by a sequential flow experiment leading to a library of eight enantioenriched diketone compounds. KEYWORDS : Robinson annulation, Continuous flow, Heterogeneized catalysts, Wieland-Miescher ketone, Hajos-Parrish ketoneThe Hajos-Parrish-Eder-Sauer-Wiechert (H-P-E-S-W) reaction to access chiral bicyclic enones, via an intramolecular aldol reaction, is one of the most well-known organocatalytic processes. 1 Reported in 1971 by two independent industrial research groups, this L-proline-catalyzed process enables the isolation of enantioenriched Wieland-Miescher (W-M, 1) and Hajos-Parrish (H-P, 2) ketones (Figure 1). 2 While high enantioselectivity was achieved for the H-P ketone (2), the W-M ketone (1) was obtained with moderate enantioselectivity. In both cases, prolonged reaction times were required. Enantioenriched W-M and H-P ketones provide access to a broad variety of sesquiterpenoids, diterpenoids and steroids. 1b,3 Biological activities of these compounds include antimicrobial, anticancer, antiviral and antineurodegenerative effects. 3 For these reasons, since 2000, following the seminal work by List and Barbas on the use of proline as a catalyst for enantioselective aldol reaction, 4 there has been a resurgent interest in achieving more efficient routes for these catalytic processes. 5 As a result, several new organocatalysts have emerged for the synthesis of these bicyclic enones. 3a-b Among them, most structures ...

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“…As regards the preparation of the Swaminathan ketone 3, in 2016 Uwai et al proposed an asymmetric lipase-catalysed synthesis of (S)-3, as well as (S)-1 and (S)-2. However, these compounds were obtained with low enantioselectivity (8% ee for (S)-3) [107]. After that, in 2017 Pericàs and co-workers applied the PS-supported organocatalyst C-64 (in the optimized conditions discussed in the paragraph 2.2) also in the one-pot Robinson annulation for the synthesis of (R)-3, starting directly from the dione 72 (Scheme 3, n = 3, R 1 = CH 3, R 2 = H) and the MVK [97].…”

Section: Bicyclo[540]undecane Derviativesmentioning

confidence: 98%

Organocatalyst Design for the Stereoselective Annulation towards Bicyclic Diketones and Analogues

et al. 2022

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The Wieland–Miescher ketone, Hajos–Parrish–Eder–Sauer–Wiechert ketone, and their analogues are bicyclic diketones essential as building blocks for the synthesis of several natural and bioactive molecules. For this reason, since 1971, when Hajos and Parrish and Eder, Sauer, and Wiechert reported the stereoselective synthesis of these compounds promoted by L-proline, numerous methodologies and organocatalysts have been studied over the years with the aim of identifying increasingly efficient asymmetrical syntheses of these bicyclic ketones. This review will outline the methodological and stereochemical features of the organocatalytic stereoselective synthesis of these bicyclic scaffolds based on the different organocatalysts employed from 1971 until today. Particular emphasis will be given to the structural features of the catalysts and to the reaction conditions.

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Lipase-catalyzed domino Michael–aldol reaction of 2-methyl-1,3-cycloalkanedione and methyl vinyl ketone for the synthesis of bicyclic compounds

Cited by 13 publications

References 27 publications

Promiscuity of Lipase‐Catalyzed Reactions for Organic Synthesis: A Recent Update

Promiscuity of Lipase‐Catalyzed Reactions for Organic Synthesis: A Recent Update

A Highly Active Polymer-Supported Catalyst for Asymmetric Robinson Annulations in Continuous Flow

Organocatalyst Design for the Stereoselective Annulation towards Bicyclic Diketones and Analogues

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