The Journal of Organic Chemistry
ARTICLE
4,4,5,5-Tetramethyl-2-(4-(methylthio)phenyl)-1,3,2-diox-
aborolane (12a).21. A solution of 4-(methylthio)phenylboronic acid
(400 mg, 2.38 mmol) and pinacol (281 mg, 2.38 mmol) in toluene
(50 mL) was refluxed overnight. Then, molecular sieves (3 Å, 50 mg)
were added, and the reaction mixture was stirred for an additional 2 h.
After cooling to rt, the reaction mixture was filtered, and the solvent was
evaporated to give a pale yellow solid. The residue was purified by
column chromatography (SiO2; n-hexane/EtOAc, 2:1) to give 8 as a
of peaks of the product and the starting material. Only one product was
observed by NMR. 1H NMR (400 MHz, CDCl3) δ 1.38ꢀ1.41 (m, 2H),
1.57ꢀ1.61 (m, 2H), 1.81ꢀ1.88 (m, 4H), 2.73 (s, 3H), 4.71 (m, 2H),
7.58 (d, J = 8 Hz, 2H), 7.88 (d, J = 12.0 Hz, 2H). 13C NMR (100 MHz,
CDCl3) δ 19.9, 29.2, 44.3, 76.0, 126.0, 136.1, 144.0.
’ ASSOCIATED CONTENT
1
white solid (560 mg, 94%). H NMR (200 MHz, CDCl3) δ 1.34 (s,
S
Supporting Information. Experimental procedures,
12 H), 2.49 (s, 3H), 7.22 (d, J = 10 Hz, 2H), 7.71 (d, J = 8.2 Hz, 2H). 13C
NMR (100 MHz, CDCl3) δ 15.0, 24.8, 83.7, 125.0, 135.1, 142.5. Anal.
Calcd for C13H19BO2S: C, 62.41; H, 7.66. Found: C, 62.09; H, 7.61. Mp
35.1ꢀ35.9 °C. IR (KBr): 437, 493, 519, 578, 652, 730, 817, 857, 960,
1018, 1103, 1144, 1211, 1265, 1359, 1394, 1433, 1545, 1596, 2926,
b
synthesis of substrates, 1H NMR, 13C NMR, and 31P NMR, XPS,
mass spectrometry, FT-IR, and X-ray crystallography data. This ma-
org.
2977 cmꢀ1
.
’ AUTHOR INFORMATION
4,4,5,5-Tetramethyl-2-(4-(methylsulfinyl)phenyl)-1,3,2-diox-
aborolane (12b). 1H NMR (500 MHz, CD3CN) δ 1.34 (s, 12 H),
2.67 (s, 3H), 7.64 (d, J = 25.0 Hz, 2H), 7.86 (d, J = 20.0 Hz, 2H). 13C
NMR (125 MHz, CD3CN) δ 25.1, 44.2, 85.2, 110.2, 123.7, 136.0, 150.9.
MS (CIþ): m/z 267 (MHþ). HRMS (CIþ) m/z calcd for C13H20BO3S
(MHþ): 267.1148. Found: 267.1222.
Corresponding Author
’ ACKNOWLEDGMENT
4,4,5,5-Tetramethyl-2-(2-(methylthio)phenyl)-1,3,2-diox-
aborolane (13a).22. A solution of 2-(methylthio)phenylboronic acid
(400 mg, 2.38 mmol) and pinacol (281 mg, 2.38 mmol) in toluene
(50 mL) was refluxed overnight. Then, molecular sieves (3 Å, 50 mg)
were added, and the reaction mixture was stirred for additional 2 h. After
cooling to rt, the reaction mixture was filtered, and the solvent was
evaporated to give a pale yellow liquid. The residue was purified by
column chromatography (SiO2; n-Hexane/EtOAc, 2:1) to give 9 as a
colorless liquid (571 mg, 96%). 1H NMR (400 MHz, CDCl3) δ 1.37 (s,
12 H), 2.45 (s, 3H), 7.10 (dt, J = 1.2 Hz, J = 7.4 Hz, 1H), 7.17 (d,
J = 7.6 Hz, 1H), 7.36 (dt, J = 1.6 Hz, J = 7.8 Hz, 1H), 7.68 (dd, J = 1.6 Hz,
J = 7.2 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 15.7, 24.8, 83.9, 123.6,
123.8, 131.1, 135.8, 145.1. Supersonic GC-MS (EIþ) m/z calcd for
C13H19BO2S (Mþ): 250.1. Anal. Calcd. for C13H19BO2S: C, 62.41; H,
7.66; S, 12.82. Found: C, 62.60; H, 7.54; S, 12.30. Mp 77.5ꢀ78.6 °C. IR
(KBr): 498, 576, 652, 698, 737, 764, 823, 856, 957, 1046, 1103, 1139,
We are grateful to Prof. Aviv Amirav for the GC-MS analyses
and to Dr. Shimon Hauptman and Dr. Noam Tal for the HRMS
analyses. We thank Dr. Shmuel Cohen for the X-ray crystal-
lography. We thank the Israeli Ministry of Science and Technol-
ogy for the “Eshkol” scholarship, the Marian Gertner Institute
for Medical Nanosystems for their scholarship, and Tel Aviv
University financial support.
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4,4,5,5-Tetramethyl-2-(2-(methylsulfinyl)phenyl)-1,3,2-diox-
aborolane (13b). 1H NMR (500 MHz, CD3CN) δ 1.33 (s, 12 H),
2.69 (s, 3H), 7.51 (t, J = 5.0 Hz, 1H), 7.68 (t, J = 10.0 Hz, 1H), 7.77 (d,
J = 5.0 Hz, 1H), 7.93 (J = 5.0 Hz, 1H). 13C NMR (125 MHz, CD3CN) δ
25.2, 44.8, 85.4, 123.2, 130.8, 132.7, 136.3, 153.8. MS (CIþ): m/z 267
(MHþ). Mp 59.0ꢀ60.2 °C. IR (KBr): 513, 543, 647, 699, 741, 767, 800,
856, 965, 1026, 1095, 1144, 1262, 1353, 1431, 1474, 1590, 1652, 2361,
2966, 3049 cmꢀ1
.
(3aR,7aS)-2-(4-(Methylthio)phenyl)hexahydrobenzo-[d]-
[1,3,2]dioxaborole (14a). A solution of 4-(methylthio)phenylbo-
ronic acid (400 mg, 2.38 mmol) and (1R,2S)-1,2-cyclohexanediol (276 mg,
2.38 mmol) in toluene (50 mL) was refluxed overnight. Then, molecular
sieves (3 Å, 50 mg) were added, and the reaction mixture was stirred for an
additional 2 h. After cooling to rt, the reaction mixture was filtered, and the
solvent was evaporated to give a pale yellow solid. The residue was purified
by column chromatography (SiO2; n-hexane/EtOAc, 2:1) to give 10 as a
white solid (578 mg, 98%). 1H NMR (400 MHz, CDCl3) δ1.38ꢀ1.41 (m,
2 H), 1.57ꢀ1.61 (m, 2H), 1.81ꢀ1.88 (m, 4H), 2.49 (s, 3H), 4.52 (m, 2H),
7.25 (d, J = 8 Hz, 2H), 7.74 (d, J = 12.0, 2H). 13C NMR (100 MHz,
CDCl3) δ 14.6, 18.9, 28.3, 75.2, 124.6, 134.8, 142.5. MS (CIþ): m/z 249
(MHþ). HRMS (CIþ) calcd for C13H17BO2S (MHþ): 249.1121. Found:
249.1100.
(3aR,7aS)-2-(4-(Methylsulfinyl)phenyl)hexahydrobenzo-
[d]-[1,3,2]dioxaborole (14b). This compound was not stable en-
ough to undergo a column chromatography or any other examined
purification technique. The yield was estimated by 1H NMR integration
5245
dx.doi.org/10.1021/jo2001808 |J. Org. Chem. 2011, 76, 5240–5246