Synthesis of Polydiynes via an Unexpected Dimerization/Polymerization Sequence of C3 Propargylic Electrophiles
Here, we describe the unexpected discovery of a Cu-catalyzed condensation polymerization reaction of propargylic electrophiles (CPPE) that transforms simple C3 building blocks into polydiynes of C6 repeating units. This reaction was achieved by a simple system composed of a copper acetylide initiator and an electron-rich phosphine ligand. Alkyne polymers (up to 33.8 kg/mol) were produced in good yields and exclusive regioselectivity with high functional group compatibility. Hydrogenation of the product afforded a new polyolefin-type backbone, while base-mediated isomerization led to a new type of dienyne-based electron-deficient conjugated polymer. Mechanistic studies revealed a new α-α selective Cu-catalyzed dimerization pathway of the C3 unit, followed by in situ organocopper-mediated chain-growth propagation. These insights not only provide an important understanding of the Cu-catalyzed CPPE of C3, C4, and C6 monomers in general but also lead to a significantly improved synthesis of polydiynes from simpler starting materials with handles for the incorporation of an α-end functional group.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2022 |
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| Erschienen: |
2022 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:144 |
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| Enthalten in: |
Journal of the American Chemical Society - 144(2022), 19 vom: 18. Mai, Seite 8807-8817 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Sun, Han-Li [VerfasserIn] |
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| Links: |
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| Themen: |
789U1901C5 |
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| Anmerkungen: |
Date Completed 19.05.2022 Date Revised 01.06.2022 published: Print-Electronic Citation Status MEDLINE |
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| doi: |
10.1021/jacs.2c02816 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM340507489 |
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| 245 | 1 | 0 | |a Synthesis of Polydiynes via an Unexpected Dimerization/Polymerization Sequence of C3 Propargylic Electrophiles |
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| 500 | |a Date Revised 01.06.2022 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status MEDLINE | ||
| 520 | |a Here, we describe the unexpected discovery of a Cu-catalyzed condensation polymerization reaction of propargylic electrophiles (CPPE) that transforms simple C3 building blocks into polydiynes of C6 repeating units. This reaction was achieved by a simple system composed of a copper acetylide initiator and an electron-rich phosphine ligand. Alkyne polymers (up to 33.8 kg/mol) were produced in good yields and exclusive regioselectivity with high functional group compatibility. Hydrogenation of the product afforded a new polyolefin-type backbone, while base-mediated isomerization led to a new type of dienyne-based electron-deficient conjugated polymer. Mechanistic studies revealed a new α-α selective Cu-catalyzed dimerization pathway of the C3 unit, followed by in situ organocopper-mediated chain-growth propagation. These insights not only provide an important understanding of the Cu-catalyzed CPPE of C3, C4, and C6 monomers in general but also lead to a significantly improved synthesis of polydiynes from simpler starting materials with handles for the incorporation of an α-end functional group | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Research Support, Non-U.S. Gov't | |
| 650 | 7 | |a Alkynes |2 NLM | |
| 650 | 7 | |a Polymers |2 NLM | |
| 650 | 7 | |a Copper |2 NLM | |
| 650 | 7 | |a 789U1901C5 |2 NLM | |
| 700 | 1 | |a Wu, Bin |e verfasserin |4 aut | |
| 700 | 1 | |a Liu, Da-Qi |e verfasserin |4 aut | |
| 700 | 1 | |a Yu, Zi-Di |e verfasserin |4 aut | |
| 700 | 1 | |a Wang, Jun-Jie |e verfasserin |4 aut | |
| 700 | 1 | |a Liu, Qianyi |e verfasserin |4 aut | |
| 700 | 1 | |a Liu, Xingchen |e verfasserin |4 aut | |
| 700 | 1 | |a Niu, Dawen |e verfasserin |4 aut | |
| 700 | 1 | |a Dou, Jin-Hu |e verfasserin |4 aut | |
| 700 | 1 | |a Zhu, Rong |e verfasserin |4 aut | |
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