Arylboronic Acid Pinacol Esters as Stable Boron Sources for Dihydrodibenzoborepin Derivatives and a Dibenzoborole
Abstract
:1. Introduction
2. Results and Discussion
2.1. Synthetic Studies
2.2. Single-Crystal X-ray Diffraction Analysis
2.3. Photophysical Properties and Theoretical Calculations
3. Materials and Method
3.1. General Considerations
3.2. Preparation of 2Mg-sp3
3.3. Synthesis of 5-(9-Anthryl)-5H-9,10-dihydrodibenzo[b,f]borepin (1-sp3) Using AnthBpin
3.4. Synthesis of 5-(2,4,6-Trimethylphenyl)-5H-9,10-dihydrodibenzo[b,f]borepin (3)
3.5. Synthesis of 5-(2,4,6-Triisopropylphenyl)-5H-9,10-dihydrodibenzo[b,f]borepin (4)
3.6. Synthesis of 5-(10-Bromo-9-anthryl)-5H-9,10-dihydrodibenzo[b,f]borepin (5-sp3)
3.7. Synthesis of 9,10-Bis(5H-9,10-Dihydrodibenzo[b,f]borepin-5-yl)anthracene (6-sp3)
3.8. Synthesis of 5-sp2 from 5-sp3
3.9. Synthesis of 1-sp2 from 5-sp2
3.10. Synthesis of 7
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Entry | Boron Source | Nucleophile | Conditions | Yield |
---|---|---|---|---|
1 | AnthBpin | 2Li-sp2 | C6H6/Et2O, 5 °C to r.t., overnight | 1-sp2 (–) |
2 | AnthBpin | 2Li-sp3 | C6H6/Et2O, 5 °C to r.t., overnight | 1-sp3 (–) |
3 | AnthBpin | 2Mg-sp3 | THF, reflux, overnight | 1-sp3 (62%) |
4 | AnthB(OMe)2 | 2Mg-sp3 | THF, reflux, overnight | 1-sp3 (31%) |
5 | AnthBpin | 2Mg-sp2 a | THF, reflux, overnight | 1-sp2 (–) |
3 | 5-sp3 | 6-sp3 | |
---|---|---|---|
B1–C1/C6 | 1.5682(18)/ 1.5706(19) | 1.562(5)/ 1.567(5) | 1.572(3)/ 1.569(4) |
B1–C15 | 1.5866(17) | 1.592(5) | 1.594(3) |
C1–B1–C15–C16 | 89.80(14) | 89.2(4) | 80.2(2) |
C1–C2–C5–C6 | 19.1(1) | 20.2(6) | 18.9(2) |
Solvent | λabs/nm (ε) | λemi/nm | Stokes Shift/cm−1 | |
---|---|---|---|---|
1-sp3 | hexane | 385 (9300), 366 (10,000), 348 (8300) | 380, 400, 425, 446 | 3550 |
toluene | 388 (9300), 369 (11,000), 351 (8400) | 385, 407, 431, 487 | 5240 | |
THF | 387 (9700), 367 (11,000), 350 (8400) | 382, 404, 426, 503 | 5960 | |
CHCl3 | 389 (7200), 369 (8300), 348 (6800) | 384, 407, 430, 508 | 6020 | |
CH2Cl2 | 388 (9400), 369 (10,000), 351 (6900) | 441, 513 | 6280 | |
1-sp2 | hexane | 388 (14000), 368 (10,000), 350 (3900), 327 (16,000), 313 (8600) | 432, 451 | 3600 |
toluene | 391 (17,000), 371 (13,000), 353 (6400), 330 (21,000), 316 (14,000) | 471 | 4340 | |
THF | 390 (15,000), 370 (12,000), 352 (5400), 329 (18,000), 315 (10,000) | 410, 425 | 2110 | |
CHCl3 | 391 (15,000), 372 (13,000), 353 (9100), 330 (22,000), 316 (16,000) | 489 | 5130 | |
CH2Cl2 | 391 (12,000), 371 (9200), 353 (4000), 330 (14,000), 316 (8700) | 432, 496 | 5410 | |
6-sp3 | CH2Cl2 | 398 (9300), 378 (10,000), 360 (7900) | 532 | 6330 |
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Kawaguchi, H.; Fuse, K.; Maeda, N.; Kuwabara, T. Arylboronic Acid Pinacol Esters as Stable Boron Sources for Dihydrodibenzoborepin Derivatives and a Dibenzoborole. Molecules 2024, 29, 4024. https://doi.org/10.3390/molecules29174024
Kawaguchi H, Fuse K, Maeda N, Kuwabara T. Arylboronic Acid Pinacol Esters as Stable Boron Sources for Dihydrodibenzoborepin Derivatives and a Dibenzoborole. Molecules. 2024; 29(17):4024. https://doi.org/10.3390/molecules29174024
Chicago/Turabian StyleKawaguchi, Himeko, Kotomi Fuse, Nanoka Maeda, and Takuya Kuwabara. 2024. "Arylboronic Acid Pinacol Esters as Stable Boron Sources for Dihydrodibenzoborepin Derivatives and a Dibenzoborole" Molecules 29, no. 17: 4024. https://doi.org/10.3390/molecules29174024