Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
Review
. 2022 Oct 8;27(19):6701.
doi: 10.3390/molecules27196701.

Application of Biobased Solvents in Asymmetric Catalysis

Margherita Miele  1 , Veronica Pillari  2 , Vittorio Pace  1   2 , Andrés R Alcántara  3 , Gonzalo de Gonzalo  4
Affiliations
Review

Application of Biobased Solvents in Asymmetric Catalysis

Margherita Miele et al. Molecules. .

Abstract

The necessity of more sustainable conditions that follow the twelve principles of Green Chemistry have pushed researchers to the development of novel reagents, catalysts and solvents for greener asymmetric methodologies. Solvents are in general a fundamental part for developing organic processes, as well as for the separation and purification of the reaction products. By this reason, in the last years, the application of the so-called green solvents has emerged as a useful alternative to the classical organic solvents. These solvents must present some properties, such as a low vapor pressure and toxicity, high boiling point and biodegradability, and must be obtained from renewable sources. In the present revision, the recent application of these biobased solvents in the synthesis of optically active compounds employing different catalytic methodologies, including biocatalysis, organocatalysis and metal catalysis, will be analyzed to provide a novel tool for carrying out more ecofriendly organic processes.

Keywords: biobased solvents; biocatalysis; green chemistry; metal catalysis; organocatalysis.

PubMed Disclaimer

Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Enantioenriched α-cyanocyclopropyl Grignard reagents.
Figure 2
Figure 2
Pharmacologically active homochiral analogues.
Figure 3
Figure 3
Luisi’s asymmetric reduction of ketones to alcohols under microfluidic conditions in 2-MeTHF.
Figure 4
Figure 4
Organozinc addition to a quaternary carbon center.
Figure 5
Figure 5
Biologically active substances featuring a quaternary stereocenter.
Figure 6
Figure 6
Enantioselective Cu-catalyzed hydroamination of cinnamoyl derivatives.
Figure 7
Figure 7
Enantioselective Michael-type addition of organoboranes to chalcones.
Figure 8
Figure 8
Asymmetric α-borylmethyl oxindoles from o-iodoanilides.
Figure 9
Figure 9
Synthesis of bortezomib through asymmetric Rh-catalyzed borylation of aa leucine analogue.
Figure 10
Figure 10
Combined reductive-DKR en route to syn-α-alkoxy β-hydroxyesters.
Figure 11
Figure 11
Asymmetric Ni-catalyzed alkylidene-cyclopropanes from olefines and gem-dichloroalkenes.
Figure 12
Figure 12
Chiral pyridine derivatives from functionalized malononitriles and alkynes.
Figure 13
Figure 13
Asymmetric α-benzylation of six-membered lactams in CPME.
Figure 14
Figure 14
3,3-disubstituted oxindoles via MBH-chemistry in 2-MeTHF (a,b).
Figure 15
Figure 15
Synthesis of chiral carbazole derivatives from unsaturated indolyl-aldehydes and enals.
Figure 16
Figure 16
Asymmetric CPA catalyzed of 1,2-diaryls from naphthols and benzylic alcohols.
Figure 17
Figure 17
Photocatalytic enantioselective reduction of azaarene-based ketones in CPME employing a chiral phosphoric acid (IV) and N-phenylpiperidine (V).
Figure 18
Figure 18
Heterogeneous organocatalyzed preparation of bicyclic diketones employing 2-MeTHF as biobased solvent.
Figure 19
Figure 19
Addition of α,α-dicyanoolefins to chalcones catalyzed by cinchona-based catalysts in 2-MeTHF.
Figure 20
Figure 20
(a) Organocatalyzed synthesis of (R)-warfarin in presence of biobased solvents. (b) Michael addition and cyclation of 2-(2-nitrovinyl)phenols with β-ketoesters catalyzed by squaramide IX in biobased solvents.
Figure 21
Figure 21
Kinetic resolution of racemic alcohols via lipase-catalyzed acylation with vinyl acetate in 2-MeTHF and CPME.
Figure 22
Figure 22
Chemoenzymatic cascade leading to pure chiral cyanohydrins.
Figure 23
Figure 23
Chemoenzymatic synthesis of (+)-halofunginone employing CPME for the biocatalyzed kinetic resolution.
Figure 24
Figure 24
Chemoenzymatic preparation of optically pure Ivabradine.
Figure 25
Figure 25
Lipase-catalyzed resolution of bulky alcohols using CO2-expanded 2-MeTHF.
Figure 26
Figure 26
Lipase-catalyzed resolution of several ortho-substituted 1-phenylethanols in different solvents.
Figure 27
Figure 27
(a) Lipase-catalyzed resolution of racemic tetralols using CO2-expanded 2-MeTHF, analytical scale. (b) Scaled (20 times) kinetic resolution of racemic 2-tetralol (51).
Figure 28
Figure 28
Lipase-catalyzed preparation of several 3,4-DHP-2-ones in water/2-MeTHF.
Figure 29
Figure 29
KRED-catalyzed reduction of β-ketodioxinones (55) in biphasic media.
Figure 30
Figure 30
Whole cells-catalyzed reduction of a chloroketone using 2-MeTHF as cosolvent.
Figure 31
Figure 31
Chemoenzymatic cascade for producing enantiopure halohydrin from haloalkynes in aqueous/2-MeTHF medium.
Figure 32
Figure 32
Biocatalytic cascades furnishing the four stereoisomers of 63 in CPME-based MARS system; (A) PfBAL and RADH leading to (1R,2R)-diol; (B) PfBAL and LbADH leading to (1S,2R)-diol, (C) PpBFD and RADH leading to (1R,2S)-diol and (D) PpBFD and LbADH leading to (1S,2S)-diol.
Figure 33
Figure 33
Biocatalytic cascade leading to (4S,5S)-octane-4,5-diol.
Figure 34
Figure 34
Bioreduction of different α-ketoesters employing KREDs in presence of Cyrene as cosolvent.
See this image and copyright information in PMC

References

    1. Brown J.M., Davies S.G. Chemical asymmetric synthesis. Nature. 1989;342:631–636. doi: 10.1038/342631a0. - DOI
    1. Liu Y., Han S.J., Liu W.B., Stoltz B.M. Catalytic enantioselective construction of quaternary stereocenters: Assembly of key building blocks for the synthesis of biologically active molecules. Acc. Chem. Res. 2015;48:740–751. doi: 10.1021/ar5004658. - DOI - PMC - PubMed
    1. Anil V., Karnik M.H. Stereochemistry, a Three-Dimensional Insight. 1st ed. Elsevier; Amsterdam, The Netherlands: 2021. pp. 407–463.
    1. Curzons A.D., Constable D.J.C., Mortimer D.N., Cunningham V.L. So you think your process is green, how do you know?—Using principles of sustainability to determine what is green–a corporate perspective. Green Chem. 2001;3:1–6. doi: 10.1039/b007871i. - DOI
    1. Jiménez-González C., Curzons A.D., Constable D.J.C., Cunningham V.L. Expanding GSK’s Solvent Selection Guide—Application of life cycle assessment to enhance solvent selections. Clean Technol. Environ. Policy. 2005;7:42–50. doi: 10.1007/s10098-004-0245-z. - DOI

LinkOut - more resources