Acylative Kinetic Resolution of Alcohols Using a Recyclable Polymer-Supported Isothiourea Catalyst in Batch and Flow

Neyyappadath, Rifahath M.; Chisholm, Ross; Greenhalgh, Mark D.; Rodríguez‐Escrich, Carles; Pericàs, Miquel À.; Hähner, Georg; Smith, Andrew D.

doi:10.1021/acscatal.7b04001

Cited by 39 publications

(22 citation statements)

References 63 publications

(41 reference statements)

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“…This was clearly an indication of potential practical applicability in the continuous preparation of both enantiomers of BINOL. Taking into account that the original preparation of ent ‐ 5 d provided a more highly functionalized resin ( f =0.88 mmol.g −1 ), we reasoned that the use of this particular resin could lead to an important increase in the productivity of the acylative KR. To test this possibility a new packed bed reactor was prepared with 1.0 g of ent ‐ 5 d with f =0.88 mmol.g −1 .…”

Section: Resultsmentioning

confidence: 99%

“…In 2016, we reported the preparation of a polystyrene‐supported BTM analogue which was successfully used in the domino Michael addition/cyclization reaction with excellent yields and very high enantioselectivities, and later applied to asymmetric [4+2] and [8+2] annulation reactions . More recently, in a joint effort of our laboratories, new polystyrene‐supported isothiourea catalysts, based on the homogeneous catalysts BTM and HyperBTM, have been prepared and used for the acylative KR of secondary and secondary and tertiary heterocyclic alcohols in batch and in continuous flow. However, there are currently no examples where BTM catalysts have been applied for the acylative KR of 1,1’‐bi‐2‐naphthol (BINOL).…”

Section: Introductionmentioning

confidence: 99%

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Continuous Flow Preparation of Enantiomerically Pure BINOL(s) by Acylative Kinetic Resolution

et al. 2020

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A polystyrene‐immobilized isothiourea has been applied to the enantioselective acylative kinetic resolution (KR) of monoacylated BINOL(s) with inexpensive isobutyric anhydride in batch and flow. High selectivity values (s=29 at 0 °C) and a remarkable stability of the catalytic system in the operation conditions have been recorded for unsubstituted BINOL. No significant loss of activity/selectivity is recorded after 10 consecutive KR cycles in batch. A continuous flow process has been implemented and operated with a 100 mmol (32.8 g) sample of racemic monoacetylated BINOL in dichloromethane solution in an 84 hours experiment with a packed bed reactor containing 1 g (f=0.37 mmol.g−1) of the functional resin (s=17–21). Residence time can be decreased to 10 min with the same reactor to achieve a conversion of 58% with a selectivity factor s=17 when a more highly functionalized catalyst (f=0.88 mmol.g−1) is used. This translates into a remarkable combined productivity of 5.5 mmolprod ⋅ mmolcat−1 ⋅ h−1.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Continuous Flow Preparation of Enantiomerically Pure BINOL(s) by Acylative Kinetic Resolution

et al. 2020

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“…Based on the PS‐BTM catalyst, Pericàs and colleagues also developed an immobilized PS‐HyperBTM catalyst, which was successfully applied for the acylative kinetic resolution of a range of secondary and tertiary heterocyclic alcohols in batch and flow conditions. Good to excellent selectivity values were observed …”

Section: Heterogeneous Enantioselective Catalysis In Flowmentioning

confidence: 88%

Recent Advances in Continuous‐Flow Enantioselective Catalysis

Ding

Nie

et al. 2020

Chemistry A European J

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The increased demand for more efficient, safe, and green production in fine chemical and pharmaceutical industry calls for the development of continuous-flowm anufacturing, and for chiral chemicals in particular,e nantioselective catalytic processes. In recenty ears, this emerging direction has received considerable attention and has seen rapid progress. In most cases, catalytic enantioselective flow processes using homogeneous, heterogeneous, or enzymatic catalysts have shown significant advantages over the conventional batch mode,s uch as shortened reaction times, lower catalysts loadings, andh igher selectivities in addition to the normalm erits of non-enantioselective flow operations. In this Minireview,t he advancements, key strategies, methods, and technologiesd eveloped the last six years as well as remaining challenges are summarized.[a] T.

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“…More recently, a collaboration with the group of Andrew D. Smith form the University of Saint Andrews (Scotland) has given rise to the application of 24 in the kinetic resolution of alcohols in flow . (Figure ).…”

Section: Immobilized Organocatalysts For Work In Flowmentioning

confidence: 99%

Catalytic Enantioselective Flow Processes with Solid‐Supported Chiral Catalysts

Rodríguez‐Escrich

Pericàs

2018

The Chemical Record

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Sustainability concerns are the wind in the sails for the development of novel, more selective catalytic processes. Hence, chiral catalysts play a crucial role in the green production of enantioenriched compounds. To further increase the green profile of this approach, the use of solid-supported catalytic species is appealing due to the reduced generation of waste, as well as the possibility of reusing the precious catalyst. Even more attractive is the implementation of flow processes based on these immobilized catalysts, a flexible strategy that allows to generate from milli- to multi-gram amounts of chiral product with a reduced footprint set-up. Herein, we will present the efforts devoted in our laboratory towards the immobilization of chiral catalysts and their use in single-pass, highly enantioselective, flow processes. Proline, diarylprolinols, other aminocatalysts, squaramides, thioureas, phosphoric acids and even chiral ligands and metal-based catalysts constitute our current toolkit of supported species for enantioselective catalysis.

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Acylative Kinetic Resolution of Alcohols Using a Recyclable Polymer-Supported Isothiourea Catalyst in Batch and Flow

Cited by 39 publications

References 63 publications

Continuous Flow Preparation of Enantiomerically Pure BINOL(s) by Acylative Kinetic Resolution

Continuous Flow Preparation of Enantiomerically Pure BINOL(s) by Acylative Kinetic Resolution

Recent Advances in Continuous‐Flow Enantioselective Catalysis

Catalytic Enantioselective Flow Processes with Solid‐Supported Chiral Catalysts

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