Regio‐ and Stereoselective Synthesis of 1,1‐Diborylalkenes via Brønsted Base‐Catalyzed Mixed Diboration of Alkynyl Esters and Amides with BpinBdan
Please always quote using this URN: urn:nbn:de:bvb:20-opus-214728
- The NaOtBu‐catalyzed mixed 1,1‐diboration of terminal alkynes using the unsymmetrical diboron reagent BpinBdan (pin = pinacolato; dan = 1,8‐diaminonaphthalene) proceeds in a regio‐ and stereoselective fashion affording moderate to high yields of 1,1‐diborylalkenes bearing orthogonal boron protecting groups. It is applicable to gram‐scale synthesis without loss of yield or selectivity. The mixed 1,1‐diborylalkene products can be utilized in Suzuki–Miyaura cross‐coupling reactions which take place selectivly at the C–B site. DFT calculationsThe NaOtBu‐catalyzed mixed 1,1‐diboration of terminal alkynes using the unsymmetrical diboron reagent BpinBdan (pin = pinacolato; dan = 1,8‐diaminonaphthalene) proceeds in a regio‐ and stereoselective fashion affording moderate to high yields of 1,1‐diborylalkenes bearing orthogonal boron protecting groups. It is applicable to gram‐scale synthesis without loss of yield or selectivity. The mixed 1,1‐diborylalkene products can be utilized in Suzuki–Miyaura cross‐coupling reactions which take place selectivly at the C–B site. DFT calculations suggest the NaOtBu‐catalyzed mixed 1,1‐diboration of alkynes occurs through deprotonation of the terminal alkyne, stepwise addition of BpinBdan to the terminal carbon followed by protonation with tBuOH. Experimentally observed selective formation of (Z)‐diborylalkenes is supported by our theoretical studies.…
Author: | Xiaocui Liu, Wenbo Ming, Xiaoling Luo, Alexandra Friedrich, Jan Maier, Udo Radius, Webster L. Santos, Todd B. Marder |
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URN: | urn:nbn:de:bvb:20-opus-214728 |
Document Type: | Journal article |
Faculties: | Fakultät für Chemie und Pharmazie / Institut für Anorganische Chemie |
Language: | English |
Parent Title (English): | European Journal of Organic Chemistry |
Year of Completion: | 2020 |
Volume: | 2020 |
Issue: | 13 |
First Page: | 1941 |
Last Page: | 1946 |
Source: | European Journal of Organic Chemistry 2020, 13, 1941-1946. DOI: 10.1002/ejoc.202000128 |
DOI: | https://doi.org/10.1002/ejoc.202000128 |
Dewey Decimal Classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 547 Organische Chemie |
Tag: | boronate esters; borylation; cross‐coupling; structure elucidation; synthesis design |
Release Date: | 2021/04/19 |
Licence (German): | CC BY: Creative-Commons-Lizenz: Namensnennung 4.0 International |