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Special Issue "Asymmetric Synthesis 2017"

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

Deadline for manuscript submissions: closed (31 May 2017)

Special Issue Editor

Guest Editor
Prof. Dr. Rafael Chinchilla

Department of Organic Chemistry, University of Alicante, PO Box 99, 03080 Alicante, Spain
Website | E-Mail
Interests: supported reagents; palladium-catalyzed reactions; asymmetric synthesis; organocatalysis

Special Issue Information

Dear Colleagues,

Asymmetric Synthesis is perhaps the field of the Organic Synthesis that has experienced a more impressive development in the last few decades. As the majority of therapeutics and active natural products are in one enantiomeric form, the development of asymmetric synthetic methodologies plays a crucial role in the chemical production of these compounds of interest.

In spite of all the uncountable and impressive results achieved in this area along the years, the use of asymmetric synthesis in the chemical industry is, although important, still limited. Thus, the direct modification of naturally found chiral molecules results industrially very common, although applying an asymmetric transformation could often render the final compounds from cheaper and more easily available sources. However, still there are no convenient asymmetric preparations for many types of compounds. Therefore, the development of efficient asymmetric methodologies using economical starting materials and/or catalysts, suitable to render very high or total asymmetric bias, and employing mild reaction conditions remains nowadays as a topic of the highest interest. Of course, we should add the present environmental concerns to these considerations, what means safe reagents and solvents, recyclability, etc. Therefore, asymmetric synthesis still remains as a big (but rewarding) challenge for any synthetic chemist. This Special Issue of Molecules aims to provide a broad overview of the latest developments to access stereo differentiation in the synthesis of compounds of interest.

Prof. Dr. 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 papers will be 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 monthly 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 1800 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

Published Papers (9 papers)

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Editorial

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Open AccessEditorial Special Issue: Asymmetric Synthesis 2017
Molecules 2017, 22(9), 1504; doi:10.3390/molecules22091504
Received: 6 September 2017 / Accepted: 7 September 2017 / Published: 8 September 2017
PDF Full-text (175 KB) | HTML Full-text | XML Full-text
Abstract
The use of asymmetric synthetic methodologies plays a crucial role, nowadays, in the preparation of bioactive or other interesting compounds [...]
Full article
(This article belongs to the Special Issue Asymmetric Synthesis 2017)

Research

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Open AccessArticle Enantioselective Michael Addition of Cyclic β-Diones to α,β-Unsaturated Enones Catalyzed by Quinine-Based Organocatalysts
Molecules 2017, 22(7), 1096; doi:10.3390/molecules22071096
Received: 16 May 2017 / Revised: 25 June 2017 / Accepted: 26 June 2017 / Published: 30 June 2017
Cited by 2 | PDF Full-text (1645 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
An enantioselective (52–98% ee) Michael addition between cyclic β-diones and α,β-unsaturated enones was established in the presence of quinine-based primary amine or squaramide. A variety of cinnamones were smoothly converted into the desired 3,4-dihydropyrans in moderate to high yields (63–99%). Chalcones were also
[...] Read more.
An enantioselective (52–98% ee) Michael addition between cyclic β-diones and α,β-unsaturated enones was established in the presence of quinine-based primary amine or squaramide. A variety of cinnamones were smoothly converted into the desired 3,4-dihydropyrans in moderate to high yields (63–99%). Chalcones were also suitable acceptors and gave rise to the expected adducts in satisfactory yields (31–99%). The resulting adducts readily underwent further modification to form fused 4H-pyran or 2,3-dihydrofuran. Full article
(This article belongs to the Special Issue Asymmetric Synthesis 2017)
Figures

Open AccessArticle General Methodologies Toward cis-Fused Quinone Sesquiterpenoids. Enantiospecific Synthesis of the epi-Ilimaquinone Core Featuring Sc-Catalyzed Ring Expansion
Molecules 2017, 22(7), 1041; doi:10.3390/molecules22071041
Received: 1 June 2017 / Revised: 21 June 2017 / Accepted: 21 June 2017 / Published: 24 June 2017
Cited by 1 | PDF Full-text (2921 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
A stereocontrolled approach to the cis-decalin framework of clerodane diterpenes and biologically active quinone sesquiterpenes is reported. Starting from an inexpensive optically pure tetrahydroindanone, Birch reductive alkylation builds two new contiguous chiral centers—one of which is quaternary and all-carbon-substituted. Also featured is
[...] Read more.
A stereocontrolled approach to the cis-decalin framework of clerodane diterpenes and biologically active quinone sesquiterpenes is reported. Starting from an inexpensive optically pure tetrahydroindanone, Birch reductive alkylation builds two new contiguous chiral centers—one of which is quaternary and all-carbon-substituted. Also featured is a highly regioselective diazoalkane—carbonyl homologation reaction to prepare the 6,6-bicyclic skeleton. Therein, the utility of Sc(OTf)3 as a mild catalyst for formal 1C insertion in complex settings is demonstrated. Full article
(This article belongs to the Special Issue Asymmetric Synthesis 2017)
Figures

Open AccessArticle Synthesis of Pyrrolo[1,2-a]pyrimidine Enantiomers via Domino Ring-Closure followed by Retro Diels-Alder Protocol
Molecules 2017, 22(4), 613; doi:10.3390/molecules22040613
Received: 10 March 2017 / Revised: 4 April 2017 / Accepted: 6 April 2017 / Published: 13 April 2017
Cited by 1 | PDF Full-text (1910 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
From 2-aminonorbornene hydroxamic acids, a simple and efficient method for the preparation of pyrrolo[1,2-a]pyrimidine enantiomers is reported. The synthesis is based on domino ring-closure followed by microwave-induced retro Diels-Alder (RDA) protocols, where the chirality of the desired products is transferred from
[...] Read more.
From 2-aminonorbornene hydroxamic acids, a simple and efficient method for the preparation of pyrrolo[1,2-a]pyrimidine enantiomers is reported. The synthesis is based on domino ring-closure followed by microwave-induced retro Diels-Alder (RDA) protocols, where the chirality of the desired products is transferred from norbornene derivatives. The stereochemistry of the synthesized compounds was proven by X-ray crystallography. The absolute configuration of the product is determined by the configuration of the starting amino hydroxamic acid. Full article
(This article belongs to the Special Issue Asymmetric Synthesis 2017)
Figures

Open AccessArticle A General Asymmetric Synthesis of (R)-Matsutakeol and Flavored Analogs
Molecules 2017, 22(3), 364; doi:10.3390/molecules22030364
Received: 18 January 2017 / Revised: 21 February 2017 / Accepted: 24 February 2017 / Published: 27 February 2017
Cited by 2 | PDF Full-text (1558 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
An efficient and practical synthetic route toward chiral matsutakeol and analogs was developed by asymmetric addition of terminal alkyne to aldehydes. (R)-matsutakeol and other flavored substances were feasibly synthesized from various alkylaldehydes in high yield (up to 49.5%, in three steps)
[...] Read more.
An efficient and practical synthetic route toward chiral matsutakeol and analogs was developed by asymmetric addition of terminal alkyne to aldehydes. (R)-matsutakeol and other flavored substances were feasibly synthesized from various alkylaldehydes in high yield (up to 49.5%, in three steps) and excellent enantiomeric excess (up to >99%). The protocols may serve as an alternative asymmetric synthetic method for active small-molecule library of natural fatty acid metabolites and analogs. These chiral allyl alcohols are prepared for food analysis and screening insect attractants. Full article
(This article belongs to the Special Issue Asymmetric Synthesis 2017)
Figures

Open AccessArticle Asymmetric Total Syntheses of Two 3-Acyl-5,6- dihydro-2H-pyrones: (R)-Podoblastin-S and (R)- Lachnelluloic Acid with Verification of the Absolute Configuration of (−)-Lachnelluloic Acid
Molecules 2017, 22(1), 69; doi:10.3390/molecules22010069
Received: 20 November 2016 / Accepted: 25 December 2016 / Published: 1 January 2017
Cited by 1 | PDF Full-text (1563 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Expedient asymmetric total syntheses of both (R)-podoblastin-S and (R)-lachnelluloic acid, representative of natural 3-acyl-5,6-dihydro-2H-pyran-2-ones, were performed. Compared with the reported total synthesis of (R)-podoblastin-S (14 steps, overall 5% yield), the present study was achieved in only five
[...] Read more.
Expedient asymmetric total syntheses of both (R)-podoblastin-S and (R)-lachnelluloic acid, representative of natural 3-acyl-5,6-dihydro-2H-pyran-2-ones, were performed. Compared with the reported total synthesis of (R)-podoblastin-S (14 steps, overall 5% yield), the present study was achieved in only five steps in an overall 40% yield and with 98% ee (HPLC analysis). In a similar strategy, the first asymmetric total synthesis of the relevant (R)-lachnelluloic acid was achieved in an overall 40% yield with 98% ee (HPLC analysis). The crucial step utilized readily accessible and reliable Soriente and Scettri’s Ti(OiPr)4/(S)-BINOL‒catalyzed asymmetric Mukaiyama aldol addition of 1,3-bis(trimethylsiloxy)diene, derived from ethyl acetoacetate with n-butanal for (R)- podoblastin-S and n-pentanal for (R)-lachnelluloic acid. With the comparison of the specific rotation values between the natural product and the synthetic specimen, the hitherto unknown absolute configuration at the C(6) position of (−)-lachnelluloic acid was unambiguously elucidated as 6R. Full article
(This article belongs to the Special Issue Asymmetric Synthesis 2017)
Figures

Open AccessCommunication Sugar-Annulated Oxazoline Ligands: A Novel Pd(II) Complex and Its Application in Allylic Substitution
Molecules 2016, 21(12), 1704; doi:10.3390/molecules21121704
Received: 25 October 2016 / Revised: 1 December 2016 / Accepted: 7 December 2016 / Published: 10 December 2016
Cited by 3 | PDF Full-text (3503 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Two novel carbohydrate-derived pyridyl (PYOX)- and cyclopropyl (CYBOX)-substituted oxazoline ligands were prepared from d-glucosamine hydrochloride and 1,3,4,6-tetra-O-acetyl-2-amino-2-deoxy-β-d-glucopyranose hydrochloride in two steps, respectively. The sugar-annulated PYOX ligand formed a stable metal complex with Pd(II), which was fully characterized by
[...] Read more.
Two novel carbohydrate-derived pyridyl (PYOX)- and cyclopropyl (CYBOX)-substituted oxazoline ligands were prepared from d-glucosamine hydrochloride and 1,3,4,6-tetra-O-acetyl-2-amino-2-deoxy-β-d-glucopyranose hydrochloride in two steps, respectively. The sugar-annulated PYOX ligand formed a stable metal complex with Pd(II), which was fully characterized by NMR spectroscopy and X-ray crystallography. NMR and X-ray analysis revealed a change of the conformation in the sugar moiety upon complexation with the palladium(II) species. Both glycosylated ligands resulted in high asymmetric induction (up to 98% ee) upon application as chiral ligands in the Pd-catalyzed allylic alkylation of rac-1,3-diphenylallyl acetate with dimethyl malonate (Tsuji-Trost reaction). Both ligands provided mainly the (R)-enantiomer of the alkylation product. Full article
(This article belongs to the Special Issue Asymmetric Synthesis 2017)
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Review

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Open AccessReview Recent Advances in Substrate-Controlled Asymmetric Cyclization for Natural Product Synthesis
Molecules 2017, 22(7), 1069; doi:10.3390/molecules22071069
Received: 28 May 2017 / Accepted: 21 June 2017 / Published: 26 June 2017
Cited by 1 | PDF Full-text (4135 KB) | HTML Full-text | XML Full-text
Abstract
Asymmetric synthesis of naturally occurring diverse ring systems is an ongoing and challenging research topic. A large variety of remarkable reactions utilizing chiral substrates, auxiliaries, reagents, and catalysts have been intensively investigated. This review specifically describes recent advances in successful asymmetric cyclization reactions
[...] Read more.
Asymmetric synthesis of naturally occurring diverse ring systems is an ongoing and challenging research topic. A large variety of remarkable reactions utilizing chiral substrates, auxiliaries, reagents, and catalysts have been intensively investigated. This review specifically describes recent advances in successful asymmetric cyclization reactions to generate cyclic architectures of various natural products in a substrate-controlled manner. Full article
(This article belongs to the Special Issue Asymmetric Synthesis 2017)
Figures

Scheme 1

Open AccessFeature PaperReview Recent Advances in Asymmetric Organocatalyzed Conjugate Additions to Nitroalkenes
Molecules 2017, 22(6), 895; doi:10.3390/molecules22060895
Received: 11 May 2017 / Revised: 26 May 2017 / Accepted: 26 May 2017 / Published: 29 May 2017
Cited by 4 | PDF Full-text (14036 KB) | HTML Full-text | XML Full-text
Abstract
The asymmetric conjugate addition of carbon and heteroatom nucleophiles to nitroalkenes is a very interesting tool for the construction of highly functionalized synthetic building blocks. Thanks to the rapid development of asymmetric organocatalysis, significant progress has been made during the last years in
[...] Read more.
The asymmetric conjugate addition of carbon and heteroatom nucleophiles to nitroalkenes is a very interesting tool for the construction of highly functionalized synthetic building blocks. Thanks to the rapid development of asymmetric organocatalysis, significant progress has been made during the last years in achieving efficiently this process, concerning chiral organocatalysts, substrates and reaction conditions. This review surveys the advances in asymmetric organocatalytic conjugate addition reactions to α,β-unsaturated nitroalkenes developed between 2013 and early 2017. Full article
(This article belongs to the Special Issue Asymmetric Synthesis 2017)
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