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Synlett 2023; 34(18): 2169-2174
DOI: 10.1055/a-2108-9895
DOI: 10.1055/a-2108-9895
cluster
Modern Boron Chemistry: 60 Years of the Matteson Reaction
N-Functionalization of 1,2-Azaborines
The research reported in this publication was supported by National Institute of General Medical Sciences, (Award Number: 'R01GM136920'), and by Boston College start-up funds. We also acknowledge the NIH-S10 (award: 1S10OD026910-01A1) and the NSF-MRI (award: CHE-2117246) for the support of Boston College’s NMR facilities.
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Abstract
General protocols for the N-functionalization of 1,2-azaborines with C(sp3), C(sp2), or C(sp) electrophiles are described. The syntheses of a new parental BN isostere of trans-stilbene and a BN isostere of a lisdexamfetamine derivative were accomplished with the developed methodology.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2108-9895.
- Supporting Information
Publication History
Received: 04 May 2023
Accepted after revision: 12 June 2023
Accepted Manuscript online:
12 June 2023
Article published online:
31 July 2023
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References and Notes
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- 16 BN-Stilbene {1-[(E)-2-Phenylvinyl]-1,2-dihydro-1,2-azaborinine} (10) In a dry box, an oven-dried 50 mL round-bottomed flask was charged with 2-benzyl-1,2-dihydro-1,2-azaborinine (7)6 (507 mg, 3.00 mmol) and toluene (15 mL), and the mixture was cooled to –30 °C. A 2.5 M solution of BuLi in hexane (1.26 mL, 3.15 mmol) was added at –30 °C, and the resulting mixture was stirred for 20 min while it slowly warmed to RT. Pd2(dba)3 (55 mg, 0.060 mmol), QPhos (170 mg, 0.240 mmol), and β-bromostyrene (476 μL, 3.60 mmol) were added, and the mixture was stirred at 85 °C for 15 h. At the completion of the reaction, the mixture was cooled to RT, then passed through an Acrodisc using CH2Cl2 as solvent. The filtrate was concentrated under reduced pressure, and the crude product was purified by column chromatography (silica gel, 2–10% CH2Cl2–pentane) to give 8 as a white solid; yield: 497 mg (61%). FTIR (thin film): 3059, 3025, 1644, 1611, 1511, 1492, 1401, 1356, 1260, 1117, 1008, 801, 751, 693, 517 cm–1. 1H NMR (500 MHz, CD2Cl2): δ = 7.70 (d, J = 14.5 Hz, 1 H), 7.60–7.54 (m, 2 H), 7.48 (d, J = 7.5 Hz, 2 H), 7.41 (t, J = 7.0 Hz, 2 H), 7.34–7.29 (m, 3 H), 7.25–7.22 (m, 2 H), 7.18–7.16 (m, 1 H), 6.65 (d, J = 14.0 Hz, 1 H), 6.58 (d, J = 11.5 Hz, 1 H), 6.40 (t, J = 7.0 Hz, 1 H), 2.91 (s, 2 H). 11B NMR (160 MHz, CD2Cl2): δ = 37.9. 13C NMR (151 MHz, CD2Cl2): δ = 143.8, 143.0, 136.4, 134.1, 133.9, 131.0 (br), 129.7, 129.4, 128.9, 128.1, 126.8, 124.9, 121.5, 111.8, 27.6 (br). HRMS (DART-TOF): m/z [M + H]+ calcd for C19H19BN: 272.16105, found: 272.16078. In a dry box, an oven-dried 20 mL microwave vial was charged with 8 (360 mg, 1.33 mmol), dodecanol (346 mg, 1.86 mmol), CuBr (19 mg, 0.13 mmol), pyridine (214 μL, 2.66 mmol), di-tert-butyl peroxide (293 mL, 1.59 mmol), and toluene (13 mL), and the mixture was stirred at 90 °C for 1 h, then cooled to RT and the solvent was removed under reduced pressure. The crude oxidized product was purified by column chromatography (silica gel 2–50% Et2O–pentane) to isolate a mixture containing the desired product and other byproducts that was used directly to the next step. In a dry box, an oven-dried 25 mL round-bottomed flask was charged with the mixture of oxidized products and Et2O (10 mL), which was then cooled to –30 °C. LAH (15 mg, 0.40 mmol) was added at –30 °C, and the mixture was stirred for 30 min. A 2.0 M solution of HCl in Et2O (395 μL, 0.790 mmol) was added at –30 °C and the mixture was stirred for 30 min while it slowly warmed to RT. The solvent was removed under reduced pressure, and the crude product was purified by column chromatography (silica gel, 100% pentane to 2% Et2O–pentane) to give 10 as a white solid; yield: 91.3 mg (38% over two steps). FTIR (thin film): 3063, 3022, 2539, 1650, 1604, 1508, 1404, 1262, 1152, 973, 755, 693, 596 cm–1. 1H NMR (500 MHz, CD2Cl2): δ = 7.68–7.64 (m, 2 H), 7.48 (d, J = 14.5 Hz, 1 H), 7.45 (t, J = 8.5 Hz, 2 H), 7.35 (t, J = 7.5 Hz, 2 H), 7.26 (t, J = 7.5 Hz, 1 H), 6.97 (d, J = 10.5 Hz, 1 H), 6.79 (d, J = 14.5 Hz, 1 H), 6.51 (t, J = 6.5 Hz, 1 H), 5.82–4.60 (br, 1 H). 11B NMR (160 MHz, CD2Cl2): δ = 33.2 (d, J = 109 Hz). 13C NMR (151 MHz, CD2Cl2): δ = 144.4, 136.9, 136.4, 134.1, 131.4 (br), 129.3, 127.9, 126.7, 118.8, 113.3. HRMS (DART-TOF): m/z [M + H]+ calcd for C12H13BN: 182.11410, found: 182.11324.
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- 20 A similar effect has been reported for the 2,1-borazaronaphthalenes, see ref. 9a.
For a study to access N-functionalized 2,1-borazaronaphthalenes, see:
For a study to utilize 1,2-azaborinin-1-yls as anionic nitrogen ligands for main group elements, see:
For select examples, see:
For selected reviews, see:
For select examples, see:
For select examples of palladium-catalyzed N-vinylation, see:
For select examples of copper-catalyzed vinylation, see:
For select examples of oxidative cross-coupling reactions, see: