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Asymmetric Synthesis 2017

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

Deadline for manuscript submissions: closed (31 May 2017) | Viewed by 52625

Special Issue 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,

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

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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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175 KiB  
Editorial
Special Issue: Asymmetric Synthesis 2017
by Rafael Chinchilla
Molecules 2017, 22(9), 1504; https://doi.org/10.3390/molecules22091504 - 08 Sep 2017
Cited by 1 | Viewed by 3403
Abstract
The use of asymmetric synthetic methodologies plays a crucial role, nowadays, in the preparation of bioactive or other interesting compounds [...]
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(This article belongs to the Special Issue Asymmetric Synthesis 2017)

Research

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1645 KiB  
Article
Enantioselective Michael Addition of Cyclic β-Diones to α,β-Unsaturated Enones Catalyzed by Quinine-Based Organocatalysts
by Qingqing Wang, Wei Wang, Ling Ye, Xuejun Yang, Xinying Li, Zhigang Zhao and Xuefeng Li
Molecules 2017, 22(7), 1096; https://doi.org/10.3390/molecules22071096 - 30 Jun 2017
Cited by 20 | Viewed by 5077
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)
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2921 KiB  
Article
General Methodologies Toward cis-Fused Quinone Sesquiterpenoids. Enantiospecific Synthesis of the epi-Ilimaquinone Core Featuring Sc-Catalyzed Ring Expansion
by Hilan Z. Kaplan, Victor L. Rendina and Jason S. Kingsbury
Molecules 2017, 22(7), 1041; https://doi.org/10.3390/molecules22071041 - 24 Jun 2017
Cited by 6 | Viewed by 5483
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)
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1910 KiB  
Article
Synthesis of Pyrrolo[1,2-a]pyrimidine Enantiomers via Domino Ring-Closure followed by Retro Diels-Alder Protocol
by Beáta Fekete, Márta Palkó, Matti Haukka and Ferenc Fülöp
Molecules 2017, 22(4), 613; https://doi.org/10.3390/molecules22040613 - 13 Apr 2017
Cited by 8 | Viewed by 4707
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)
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1558 KiB  
Article
A General Asymmetric Synthesis of (R)-Matsutakeol and Flavored Analogs
by Jia Liu, Honglian Li, Chao Zheng, Shichao Lu, Xianru Guo, Xinming Yin, Risong Na, Bin Yu and Min Wang
Molecules 2017, 22(3), 364; https://doi.org/10.3390/molecules22030364 - 27 Feb 2017
Cited by 7 | Viewed by 5922
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)
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1563 KiB  
Article
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
by Tetsuya Fujiwara, Takeshi Tsutsumi, Kohei Nakata, Hidefumi Nakatsuji and Yoo Tanabe
Molecules 2017, 22(1), 69; https://doi.org/10.3390/molecules22010069 - 01 Jan 2017
Cited by 9 | Viewed by 5651
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)
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3503 KiB  
Communication
Sugar-Annulated Oxazoline Ligands: A Novel Pd(II) Complex and Its Application in Allylic Substitution
by Jochen Kraft, Katharina Mill and Thomas Ziegler
Molecules 2016, 21(12), 1704; https://doi.org/10.3390/molecules21121704 - 10 Dec 2016
Cited by 14 | Viewed by 6124
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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4135 KiB  
Review
Recent Advances in Substrate-Controlled Asymmetric Cyclization for Natural Product Synthesis
by Jeyun Jo, Seok-Ho Kim, Young Taek Han, Jae-Hwan Kwak and Hwayoung Yun
Molecules 2017, 22(7), 1069; https://doi.org/10.3390/molecules22071069 - 26 Jun 2017
Cited by 1 | Viewed by 6686
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)
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Scheme 1

14036 KiB  
Review
Recent Advances in Asymmetric Organocatalyzed Conjugate Additions to Nitroalkenes
by Diego A. Alonso, Alejandro Baeza, Rafael Chinchilla, Cecilia Gómez, Gabriela Guillena, Isidro M. Pastor and Diego J. Ramón
Molecules 2017, 22(6), 895; https://doi.org/10.3390/molecules22060895 - 29 May 2017
Cited by 112 | Viewed by 8550
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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