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Development of Asymmetric Synthesis
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Development of Asymmetric Synthesis

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organic Chemistry".

Deadline for manuscript submissions: closed (30 November 2019) | Viewed by 20585

Special Issue Editor

Prof. Dr. Rafael Chinchilla

E-Mail Website
Guest Editor
Department of Organic Chemistry, Faculty of Sciences, and Institute of Organic Synthesis (ISO), University of Alicante, P.O. Box 99, 03080 Alicante, Spain
Interests: asymmetric synthesis; organocatalysis; solid-supported reagents; palladium-catalyzed reactions
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The search for new methodologies leading to the preparation of enantiopure compounds remains extremely active in the field of Organic Synthesis. Thus, the development of new useful asymmetric synthesis approaches results very rewarding, as many therapeutically interesting products are in one enantiomeric form.

Uncountable asymmetric procedures for the synthesis of all kind of compounds have been reported until now, but still plenty of work is necessary to develop convenient, useful, and easily scalable methodologies applicable to the preparation of many structures and also suitable to produce a sufficiently high asymmetric bias. In addition, economic considerations, such as the use of cheap and easily available sources, and, particularly nowadays, environmental considerations, such as the use of safe reagents, catalysts, and solvents, as well as their possible recyclability, are crucial. Therefore, many challenges remain to be confronted.

This Special Issue of Molecules aims to provide a broad overview of the new developments in the use of asymmetric synthesis for the preparation of compounds of interest.

Prof. Rafael Chinchilla
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Asymmetric catalysis
  • Enantioselective organocatalysis
  • Diastereoselective synthesis
  • Asymmetric biocatalysis
  • Chiral auxiliaries
  • Chiral pool synthesis
  • Chirality determination

Published Papers (7 papers)

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Editorial

Jump to: Research

2 pages, 171 KiB  
Editorial
Special Issue: Development of Asymmetric Synthesis
by Rafael Chinchilla
Molecules 2020, 25(6), 1266; https://doi.org/10.3390/molecules25061266 - 11 Mar 2020
Viewed by 1667
Abstract
Biological systems usually respond differently to enantiomers of a chiral molecule due to the inherent chirality of the active receptor sites of enzymes in nature [...] Full article
(This article belongs to the Special Issue Development of Asymmetric Synthesis)

Research

Jump to: Editorial

9 pages, 2308 KiB  
Article
Asymmetric Transfer Hydrogenation of Arylketones Catalyzed by Enantiopure Ruthenium(II)/Pybox Complexes Containing Achiral Phosphonite and Phosphinite Ligands
by Miguel Claros, Eire de Julián, Josefina Díez, Elena Lastra and M. Pilar Gamasa
Molecules 2020, 25(4), 990; https://doi.org/10.3390/molecules25040990 - 23 Feb 2020
Cited by 3 | Viewed by 2529
Abstract
A family of complexes of the formula trans-[RuCl2(L)(R-pybox)] (R-pybox = (S,S)-iPr-pybox, (R,R)-Ph-pybox, L = monodentate phosphonite, PPh(OR)2, and phosphinite, L = PPh2(OR), ligands) were screened in [...] Read more.
A family of complexes of the formula trans-[RuCl2(L)(R-pybox)] (R-pybox = (S,S)-iPr-pybox, (R,R)-Ph-pybox, L = monodentate phosphonite, PPh(OR)2, and phosphinite, L = PPh2(OR), ligands) were screened in the catalytic asymmetric transfer hydrogenation of acetophenone, observing a strong influence of the nature of both the R-pybox substituents and the L ligand in the process. The best results were obtained with complex trans-[RuCl2{PPh2(OEt)}{(R,R)-Ph-pybox}] (2c), which provided high conversion and enantioselectivity (up to 96% enantiomeric excess, e.e.) for the reduction of a variety of aromatic ketones, affording the (S)-benzylalcohols. Full article
(This article belongs to the Special Issue Development of Asymmetric Synthesis)
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16 pages, 3955 KiB  
Article
Divergent Asymmetric Total Synthesis of All Four Pestalotin Diastereomers from (R)-Glycidol
by Mizuki Moriyama, Kohei Nakata, Tetsuya Fujiwara and Yoo Tanabe
Molecules 2020, 25(2), 394; https://doi.org/10.3390/molecules25020394 - 17 Jan 2020
Cited by 7 | Viewed by 3481
Abstract
All four chiral pestalotin diastereomers were synthesized in a straightforward and divergent manner from common (R)-glycidol. Catalytic asymmetric Mukaiyama aldol reactions of readily-available bis(TMSO)diene (Chan’s diene) with (S)-2-benzyloxyhexanal derived from (R)-glycidol produced a syn-aldol adduct with [...] Read more.
All four chiral pestalotin diastereomers were synthesized in a straightforward and divergent manner from common (R)-glycidol. Catalytic asymmetric Mukaiyama aldol reactions of readily-available bis(TMSO)diene (Chan’s diene) with (S)-2-benzyloxyhexanal derived from (R)-glycidol produced a syn-aldol adduct with high diastereoselectivity and enantioselectivity using a Ti(iOPr)4/(S)-BINOL/LiCl catalyst. Diastereoselective Mukaiyama aldol reactions mediated by catalytic achiral Lewis acids directly produced not only a (1′S,6S)-pyrone precursor via the syn-aldol adduct using TiCl4, but also (1′S,6R)-pyrone precursor via the antialdol adduct using ZrCl4, in a stereocomplementary manner. A Hetero-Diels-Alder reaction of similarly available mono(TMSO)diene (Brassard’s diene) with (S)-2-benzyloxyhexanal produced the (1′S,6S)-pyrone precursor promoted by Eu(fod)3 and the (1′S,6R)-pyrone precursor Et2AlCl. Debenzylation of the (1′S,6S)-precursor and the (1′S,6R)-precursor furnished natural (−)-pestalotin (99% ee, 7 steps) and unnatural (+)-epipestalotin (99% ee, 7 steps), respectively. Mitsunobu inversions of the obtained (−)-pestalotin and (+)-epipestalotin successfully produced the unnatural (+)-pestalotin (99% ee, 9 steps) and (−)-epipestalotin (99% ee, 9 steps), respectively, in a divergent manner. All four of the obtained chiral pestalotin diastereomers possessed high chemical and optical purities (optical rotations, 1H-NMR, 13C-NMR, and HPLC measurements). Full article
(This article belongs to the Special Issue Development of Asymmetric Synthesis)
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15 pages, 1092 KiB  
Article
Preparative Method for Asymmetric Synthesis of (S)-2-Amino-4,4,4-trifluorobutanoic Acid
by Jianlin Han, Ryosuke Takeda, Xinyi Liu, Hiroyuki Konno, Hidenori Abe, Takahiro Hiramatsu, Hiroki Moriwaki and Vadim A. Soloshonok
Molecules 2019, 24(24), 4521; https://doi.org/10.3390/molecules24244521 - 10 Dec 2019
Cited by 10 | Viewed by 3612
Abstract
Enantiomerically pure derivatives of 2-amino-4,4,4-trifluorobutanoic acid are in great demand as bioisostere of leucine moiety in the drug design. Here, we disclose a method specifically developed for large-scale (>150 g) preparation of the target (S)-N-Fmoc-2-amino-4,4,4-trifluorobutanoic acid. The method employs [...] Read more.
Enantiomerically pure derivatives of 2-amino-4,4,4-trifluorobutanoic acid are in great demand as bioisostere of leucine moiety in the drug design. Here, we disclose a method specifically developed for large-scale (>150 g) preparation of the target (S)-N-Fmoc-2-amino-4,4,4-trifluorobutanoic acid. The method employs a recyclable chiral auxiliary to form the corresponding Ni(II) complex with glycine Schiff base, which is alkylated with CF3–CH2–I under basic conditions. The resultant alkylated Ni(II) complex is disassembled to reclaim the chiral auxiliary and 2-amino-4,4,4-trifluorobutanoic acid, which is in situ converted to the N-Fmoc derivative. The whole procedure was reproduced several times for consecutive preparation of over 300 g of the target (S)-N-Fmoc-2-amino-4,4,4-trifluorobutanoic acid. Full article
(This article belongs to the Special Issue Development of Asymmetric Synthesis)
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13 pages, 1221 KiB  
Article
Organocatalytic Asymmetric Conjugate Addition of Aldehydes to Maleimides and Nitroalkenes in Deep Eutectic Solvents
by Alejandro Torregrosa-Chinillach, Alba Sánchez-Laó, Elisa Santagostino and Rafael Chinchilla
Molecules 2019, 24(22), 4058; https://doi.org/10.3390/molecules24224058 - 09 Nov 2019
Cited by 14 | Viewed by 2835
Abstract
A chiral primary amine-salicylamide is used as an organocatalyst for the enantioselective conjugate addition of α,α-disubstituted aldehydes to maleimides and nitroalkenes. The reactions are performed in deep eutectic solvents as reaction media at room temperature, leading to the corresponding adducts with enantioselectivities up [...] Read more.
A chiral primary amine-salicylamide is used as an organocatalyst for the enantioselective conjugate addition of α,α-disubstituted aldehydes to maleimides and nitroalkenes. The reactions are performed in deep eutectic solvents as reaction media at room temperature, leading to the corresponding adducts with enantioselectivities up to 88% (for maleimides) and 80% (for nitroalkenes). Catalyst and solvent can be recovered and reused. Full article
(This article belongs to the Special Issue Development of Asymmetric Synthesis)
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18 pages, 2783 KiB  
Article
Improved Access to Chiral Tetranaphthoazepinium-Based Organocatalysts Using Aqueous Ammonia as Nitrogen Source
by Auraya Manaprasertsak, Sorachat Tharamak, Christina Schedl, Alexander Roller and Michael Widhalm
Molecules 2019, 24(21), 3844; https://doi.org/10.3390/molecules24213844 - 25 Oct 2019
Cited by 2 | Viewed by 3197
Abstract
The class of 3,3′-diaryl substituted tetranaphthobisazepinium bromides has found wide application as highly efficient C2-symmetrical phase-transfer catalysts (PTCs, Maruoka type catalysts). Unfortunately, the synthesis requires a large number of steps and hampers the build-up of catalyst libraries which are often desired [...] Read more.
The class of 3,3′-diaryl substituted tetranaphthobisazepinium bromides has found wide application as highly efficient C2-symmetrical phase-transfer catalysts (PTCs, Maruoka type catalysts). Unfortunately, the synthesis requires a large number of steps and hampers the build-up of catalyst libraries which are often desired for screening experiments. Here, we present a more economic strategy using dinaphthoazepine 7 as the common key intermediate. Only at this stage various aryl substituents are introduced, and only two individual steps are required to access target structures. This protocol was applied to synthesize ten tetranaphthobisazepinium compounds 1a–1j. Their efficiency as PTCs was tested in the asymmetric substitution of tert-butyl 2-((diphenylmethylene)amino)acetate. Enantioselectivities up to 92% have been observed with new catalysts. Full article
(This article belongs to the Special Issue Development of Asymmetric Synthesis)
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10 pages, 1939 KiB  
Article
Asymmetric Henry Reaction of 2-Acylpyridine N-Oxides Catalyzed by a Ni-Aminophenol Sulfonamide Complex: An Unexpected Mononuclear Catalyst
by Mouxiong Liu, Dongdong Gui, Ping Deng and Hui Zhou
Molecules 2019, 24(8), 1471; https://doi.org/10.3390/molecules24081471 - 14 Apr 2019
Cited by 1 | Viewed by 2700
Abstract
The asymmetric Henry reaction of 2-acylpyridine N-oxide remains a challenge as N-oxides generally act as competitive catalyst inhibitors or displace activating ligands. A novel variable yield (up to 99%) asymmetric Henry reaction of 2-acypyridine N-oxides catalyzed by a Ni-aminophenol sulfonamide [...] Read more.
The asymmetric Henry reaction of 2-acylpyridine N-oxide remains a challenge as N-oxides generally act as competitive catalyst inhibitors or displace activating ligands. A novel variable yield (up to 99%) asymmetric Henry reaction of 2-acypyridine N-oxides catalyzed by a Ni-aminophenol sulfonamide complex with good to excellent enantioselectivity (up to 99%) has been developed. Mechanistic studies suggest that the unique properties of the electron-pairs of N-oxides for complexation with Ni makes the unexpected mononuclear complex, rather than the previously reported dinuclear complex, the active species. Full article
(This article belongs to the Special Issue Development of Asymmetric Synthesis)
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