Highly Diastereoselective Chelation-Controlled 1,3-<i>anti</i>-Allylation of (<i>S</i>)-3-(Methoxymethyl)hexanal Enabled by Hydrate of Scandium Triflate
En route to the total synthesis of (+)-Neopeltolide, we explored Lewis acid-assisted diastereoselective allylation of MOM-protected 3-hydroxylhexanal with β-(2,2-diethoxyethyl)-substituted (allyl)tributylstannane. The hydrated form of scandium triflate was found to be essential for attaining high 1,...
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MDPI AG
2021-03-01
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| author | Uladzimir S. Masiuk Iryna V. Mineyeva Dzmitry G. Kananovich |
| author_facet | Uladzimir S. Masiuk Iryna V. Mineyeva Dzmitry G. Kananovich |
| author_sort | Uladzimir S. Masiuk |
| collection | DOAJ |
| description | En route to the total synthesis of (+)-Neopeltolide, we explored Lewis acid-assisted diastereoselective allylation of MOM-protected 3-hydroxylhexanal with β-(2,2-diethoxyethyl)-substituted (allyl)tributylstannane. The hydrated form of scandium triflate was found to be essential for attaining high 1,3-<i>anti</i>-diastereoselectivity (d.r. 94:6), while the use of anhydrous catalyst resulted in a modest diastereocontrol (d.r. 76:24). The preferred 1,3-<i>anti</i>-selectivity in this transformation can be rationalized in the framework of the Reetz chelate model of asymmetric induction. The 1,3-<i>anti</i>-configuration of the product was confirmed by its conversion into the known C<sup>7</sup>-C<sup>16</sup> building block of (+)-Neopeltolide. We also report an improved protocol for the synthesis of β-(2,2-diethoxyethyl)-substituted (allyl)tributylstannane, which can be utilized as a cost-efficient bipolar isoprenoid-type C<sub>5</sub>-building block in the synthesis of natural compounds. |
| first_indexed | 2024-03-10T13:16:05Z |
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| id | doaj.art-0964f62e92c948268d2fa61c573f2983 |
| institution | Directory Open Access Journal |
| issn | 2073-8994 |
| language | English |
| last_indexed | 2024-03-10T13:16:05Z |
| publishDate | 2021-03-01 |
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| spelling | doaj.art-0964f62e92c948268d2fa61c573f29832023-11-21T10:22:56ZengMDPI AGSymmetry2073-89942021-03-0113347010.3390/sym13030470Highly Diastereoselective Chelation-Controlled 1,3-<i>anti</i>-Allylation of (<i>S</i>)-3-(Methoxymethyl)hexanal Enabled by Hydrate of Scandium TriflateUladzimir S. Masiuk0Iryna V. Mineyeva1Dzmitry G. Kananovich2Department of Organic Chemistry, Belarusian State University, Leningradskaya 14, 220050 Minsk, BelarusDepartment of Organic Chemistry, Belarusian State University, Leningradskaya 14, 220050 Minsk, BelarusDepartment of Chemistry and Biotechnology, School of Science, Tallinn University of Technology, Akadeemia Tee 15, 12618 Tallinn, EstoniaEn route to the total synthesis of (+)-Neopeltolide, we explored Lewis acid-assisted diastereoselective allylation of MOM-protected 3-hydroxylhexanal with β-(2,2-diethoxyethyl)-substituted (allyl)tributylstannane. The hydrated form of scandium triflate was found to be essential for attaining high 1,3-<i>anti</i>-diastereoselectivity (d.r. 94:6), while the use of anhydrous catalyst resulted in a modest diastereocontrol (d.r. 76:24). The preferred 1,3-<i>anti</i>-selectivity in this transformation can be rationalized in the framework of the Reetz chelate model of asymmetric induction. The 1,3-<i>anti</i>-configuration of the product was confirmed by its conversion into the known C<sup>7</sup>-C<sup>16</sup> building block of (+)-Neopeltolide. We also report an improved protocol for the synthesis of β-(2,2-diethoxyethyl)-substituted (allyl)tributylstannane, which can be utilized as a cost-efficient bipolar isoprenoid-type C<sub>5</sub>-building block in the synthesis of natural compounds.https://www.mdpi.com/2073-8994/13/3/470Reetz–Keck-type allylationstannylationLewis acidsorganotin compoundsβ-oxyaldehydesscandium triflate |
| spellingShingle | Uladzimir S. Masiuk Iryna V. Mineyeva Dzmitry G. Kananovich Highly Diastereoselective Chelation-Controlled 1,3-<i>anti</i>-Allylation of (<i>S</i>)-3-(Methoxymethyl)hexanal Enabled by Hydrate of Scandium Triflate Symmetry Reetz–Keck-type allylation stannylation Lewis acids organotin compounds β-oxyaldehydes scandium triflate |
| title | Highly Diastereoselective Chelation-Controlled 1,3-<i>anti</i>-Allylation of (<i>S</i>)-3-(Methoxymethyl)hexanal Enabled by Hydrate of Scandium Triflate |
| title_full | Highly Diastereoselective Chelation-Controlled 1,3-<i>anti</i>-Allylation of (<i>S</i>)-3-(Methoxymethyl)hexanal Enabled by Hydrate of Scandium Triflate |
| title_fullStr | Highly Diastereoselective Chelation-Controlled 1,3-<i>anti</i>-Allylation of (<i>S</i>)-3-(Methoxymethyl)hexanal Enabled by Hydrate of Scandium Triflate |
| title_full_unstemmed | Highly Diastereoselective Chelation-Controlled 1,3-<i>anti</i>-Allylation of (<i>S</i>)-3-(Methoxymethyl)hexanal Enabled by Hydrate of Scandium Triflate |
| title_short | Highly Diastereoselective Chelation-Controlled 1,3-<i>anti</i>-Allylation of (<i>S</i>)-3-(Methoxymethyl)hexanal Enabled by Hydrate of Scandium Triflate |
| title_sort | highly diastereoselective chelation controlled 1 3 i anti i allylation of i s i 3 methoxymethyl hexanal enabled by hydrate of scandium triflate |
| topic | Reetz–Keck-type allylation stannylation Lewis acids organotin compounds β-oxyaldehydes scandium triflate |
| url | https://www.mdpi.com/2073-8994/13/3/470 |
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