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Organic & Biomolecular Chemistry
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ARTICLE
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temperature for 3 hours (TLC monitoring). Reaction mixture 245 Hz, FCAr), 144.8 (CAr), 137.6 (d, 4JCF = 3 Hz, CAr),V1ie3w7A.r2tic(ledO,n4lJinCeF
3
Ar
was evaporated under reduced pressure, and continued the = 4 Hz, CAr), 134.5 (CAr), 129.8 (d, JCFD=OI:810H.1z0,39C/DH0O),B01122298.5A
procedure as described on Procedure
A
with bis(4- (CHAr),129.2 (d, 3JCF = 8 Hz, CHAr), 128.8 (CНAr), 115.7 (d, 2JCF = 21
fluorophenyl)methanol 7a (220 mg, 1 mmol) and CH2Cl2 (3 mL) Hz, CHAr), 115.5 (d, JCF = 21 Hz, CHAr), 69.6 (C(O)CHC(О)), 52.7
2
without TfOH addition. Yield 53% (223 mg).
2-(Bis(4-fluorophenyl)methyl)-4-(1-adamantyl)-1-
phenylbutane-1,3-dione (8b). Procedure A. Obtained from β- calcd. for C28H28F2O2 (M+Na+):457.1950, found: 457.1953.
diketone 4i (296 mg, 1 mmol), bis(4-fluorophenyl)methanol 7a 2-(Bis(4-fluorophenyl)methyl)-5,5-dimethyl-1-(4-
(CHAr2), 49.9 (CH2), 30.3 (C(CH3)3), 29.1 (C(CH3)3), 21.7 (CH3Ar).
19F NMR (376 MHz, CDCl3): δ = -115.46, -116.09. HRMS (ESI)
(220 mg, 1 mmol) and TfOH (28 μL, 0.3 mmol). Yield 78% (390 methoxyphenyl)butane-1,3-dione (8e). Procedure B. Obtained
mg), colorless crystal, mp 200-202 oС, Rf = 0.75 (CH2Cl2). 1H NMR from 1-(4-methoxyphenyl)ethan-1-one 3d (75 mg, 0.5 mmol),
(400 МHz, CDCl3): δ = 7.94-7.92 (m, 2H, HAr), 7.58-7.54 (m, 1H, tert-butylacetic acid 2b (58 mg, 0.5 mmol) and bis(4-
HAr), 7.46-7.42 (m, 2H, HAr), 7.34-7.31 (m, 2H, HAr), 7.18-7.14 (m, fluorophenyl)methanol 7a (110 mg, 0.5 mmol). Yield 45% (100
2H, HAr), 7.01 (t, J = 8.7 Hz, 2H, HAr), 6.82 (t, J = 8.7 Hz, 2H, HAr), mg), white solid, mp 204-207 oС. 1H NMR (400 МHz, CDCl3): δ =
5.45 (d, J = 11.9 Hz, 1H, C(O)CHC(О))*, 5.07 (d, J = 11.9 Hz, 1H, 7.94 (d, J = 8.9 Hz, 2H, HAr), 7.36-7.27 (m, 2H, HAr), 7.20-7.11 (m,
CHAr2)*, 2.25 (d, J = 17.1 Hz, 1H, CH2Ad), 2.00 (d, J = 17.1 Hz, 1H, 2H, HAr), 6.99 (t, J = 8.6 Hz, 2H, HAr), 6.90 (d,J = 8.9 Hz, 2H, HAr),
CH2Ad), 1.79 (bs, 3H, CHAd), 1.62-1.48 (m, 6H, CH2Ad), 1.38-1.29 6.82 (t, J = 8.6 Hz, 2H, HAr), 5.39 (d, J = 11.9 Hz, 1H, C(O)CHC(О)),
(m, 6H, CH2Ad). 13С NMR (100 МHz, CDCl3): δ = 202.2 (CO), 193.6 5.07(d, J = 11.9 Hz, 1H, CHAr2), 3.85(s, 3H, OCH3), 2.36(d, J = 17.9
(CO), 161.7 (d, 1JCF = 244 Hz, FCAr), 161.0 (d, 1JCF = 244 Hz, FCAr), Hz, 1H, CH2), 2.15(d, J = 17.7 Hz, 1H, CH2),0.72 (s, 9H, C(CH3)3).
4
4
137.0 (d, JCF = 3.3 Hz, CAr), 136.8 (d, JCF = 3.3 Hz, CAr), 136.7 13С NMR (100 МHz, CDCl3): δ = 203.4 (CO), 192.1 (CO), 164.1
(CAr), 133.3 (CНAr), 129.2 (d, 2JCF = 54 Hz, CHAr), 129.0 (d, 2JCF = 54 (CAr),161.7 (d, 1JCF = 246 Hz, FCAr), 161.4 (d, 1JCF = 246 Hz, FCAr),
Hz, CHAr), 128.4 (CН), 128.2 (CН), 115.3 (d, JCF = 21 Hz, CHAr), 137.7 (d, 4JCF = 3 Hz, CAr), 137.3 (d, 4JCF = 4 Hz, CAr), 131.2 (CHAr),
3
3
3
3
115.1 (d, JCF = 21 Hz, CHAr), 69.7 (C(O)CHC(О)), 53.4 (CHAr2), 130.0 (CAr),129.8 (d, JCF = 8 Hz, CHAr), 129.2 (d, JCF = 8 Hz,
49.5 (CH2Ad), 41.2 (CH2Ad), 36.2 (CH2Ad), 32.5 (CAd), 28.0 (CHAd). CHAr),115.7 (d, JCF = 21 Hz, CHAr), 115.5 (d, JCF = 21 Hz, CHAr),
Crystals suitable for RSA were obtained by recrystallization from 114.0 (CHAr), 69.5 (C(O)CHC(О)), 55.5(OCH3), 52.5(CHAr2), 49.8
CHCl3 - i-PrOH mixture. C33H32F2O2 (498.60): calcd. C 79.49, H (CH2), 30.3 (C(CH3)3), 29.1 (C(CH3)3).19F NMR (376MHz, CDCl3): δ
2
2
6.47; found C 79.11.02, H 6.71.
2-(Bis(4-fluorophenyl)methyl)-4-(1-adamantyl)-1-(2,4-
=
-115.49, -116.13. HRMS (ESI) calcd. for C28H28F2O3
(M+Na+):473.1899, found: 473.1902.
dichlorophenyl)butane-1,3-dione (8c). Procedure A. Obtained 2-(Bis(4-fluorophenyl)methyl)-5,5-dimethyl-1-(4-
from β-diketone 4j (182 mg, 0.5 mmol), bis(4- chlorophenyl)butane-1,3-dione (8f). Procedure B. Obtained
fluorophenyl)methanol 7a (110 mg, 0.5 mmol) and TfOH (22 μL, from 1-(4-chlorophenyl)ethan-1-one (77 mg, 0.5 mmol), tert-
0.25 mmol). Yield 85% (240 mg), white solid, mp 169-170 oС, Rf butylacetic acid 2b (58 mg, 0.5 mmol) and bis(4-
= 0.70 (CH2Cl2). 1H NMR (400 МHz, CDCl3): δ = 7.36 (bs, 1H, HAr), fluorophenyl)methanol 7a (110 mg, 0.5 mmol). Yield 68% (155
7.28-7.17 (m, 6H, HAr), 6.99 (t, J = 8.5 Hz, 2H, HAr), 6.89 (t, J = 8.5 mg), white solid, mp 203-205 oС. 1H NMR (400 МHz, CDCl3): δ =
Hz, 2H, HAr), 5.27 (d, J = 11.9 Hz, 1H, C(O)CHC(О))*, 4.90 (d, J = 7.87 (d, J = 8.7 Hz, 2H, HAr), 7.40 (d, J = 8.7 Hz, 2H, HAr), 7.34-7.27
11.9 Hz, 1H, C(O)CHC(О)), 2.17 (d, J = 17.6 Hz, 1H, CH2Ad), 2.03 (m, 2H, HAr), 7.17-7.10 (m,2H, HAr), 7.00 (t, J = 8.7 Hz, 2H, HAr),
(d, J = 17.6 Hz, 1H, CH2Ad), 1.81 (bs, 3H, CHAd), 1.62-1.50 (m, 6H, 6.83 (t, J = 8.7 Hz, 2H, HAr), 5.37 (d, J = 12.1 Hz, 1H, C(O)CHC(О)),
CH2Ad), 1.38-1.30 (m, 6H, CH2Ad). 13С NMR (100 МHz, CDCl3): δ = 5.05(d, J = 11.9 Hz, 1H, CHAr2), 2.35(d, J = 17.7 Hz, 1H, CH2),
1
201.9 (CO), 194.3 (CO), 161.4 (d, JCF = 245 Hz, FCAr), 161.2 (d, 2.15(d, J = 17.9 Hz, 1H, CH2),0.72 (s, 9H, C(CH3)3). 13С NMR (100
1JCF = 244 Hz, FCAr), 137.5 (CAr), 136.6 (d, 4JCF = 4 Hz, CAr), 136.3 МHz, CDCl3): δ = 202.9 (CO), 192.9 (CO), 161.8 (d, 1JCF = 246 Hz,
4
(CAr), 136.2 (d, JCF = 4 Hz, CAr), 132.0 (CAr), 130.2 (CНAr), 129.9 FCAr), 161.5 (d, 1JCF = 246 Hz, FCAr), 140.4 (CAr), 137.4 (d, 4JCF = 4
(CНAr), 129.3 (d, 2JCF = 16 Hz, CHAr), 129.2 (d, 2JCF = 16 Hz, CHAr), Hz, CAr), 136.8 (d, 4JCF = 4 Hz, CAr), 135.2 (CAr), 130.0 (CHAr),129.7
3
3
126.8 (CНAr), 115.3 (d, 3JCF = 13 Hz, CHAr), 115.2 (d, 3JCF = 13 Hz, (d, JCF = 8 Hz, CHAr), 129.2 (d, JCF = 8 Hz, CHAr),129.2 (CHAr),
CHAr), 72.9 (C(O)CHC(О)), 54.8 (CHAr2), 50.0 (CH2Ad), 41.2 115.8 (d, JCF = 21 Hz, CHAr), 115.6 (d, JCF = 21 Hz, CHAr), 70.1
2
2
(CH2Ad), 36.2 (CH2Ad), 32.4 (CAd), 28.0 (CHAd). C33H30Cl2F2O2 (C(O)CHC(О)), 52.6 (CHAr2), 49.9 (CH2), 30.3 (C(CH3)3), 29.1
(567.49): calcd. C 69.84, H 5.33; found C 70.02, H 5.11.
2-(Bis(4-fluorophenyl)methyl)-5,5-dimethyl-1-(4-
(C(CH3)3).19F NMR (376MHz, CDCl3): δ = -115.15, -115.67. HRMS
(ESI) calcd.for C27H25ClF2O2 (M+Na+):477.1403, found: 477.1405.
methylphenyl)butane-1,3-dione (8d). Procedure B. Obtained 2-(Bis(4-fluorophenyl)methyl)-5,5-dimethyl-1-(3-
from 1-(p-tolyl)ethan-1-one (67 mg, 0.5 mmol), tert-butylacetic chlorophenyl)butane-1,3-dione (8g). Procedure B. Obtained
acid 2b (58 mg, 0.5 mmol) and carbinol 7a (110 mg, 0.5 mmol). from 1-(3-chlorophenyl)ethan-1-one (77 mg, 0.5 mmol), tert-
o
1
Yield 29% (63 mg), white solid, mp 225-227 С. H NMR (400 butylacetic acid 2b (58 mg, 0.5 mmol) and bis(4-
МHz, CDCl3): δ = 7.84 (d, J = 8.2 Hz, 2H, HAr), 7.35-7.27 (m, 2H, fluorophenyl)methanol 7a (110 mg, 0.5 mmol). Yield 70% (160
HAr), 7.25-7.20 (m, 2H, HAr), 7.18-7.12 (m, 2H, HAr), 6.99 (t, J = mg), white solid, mp 202-204 oС. 1H NMR (400 МHz, CDCl3): δ =
8.6 Hz, 2H, HAr), 6.81 (t, J = 8.5 Hz, 2H, HAr), 5.42 (d, J = 11.9 Hz, 7.87-7.84 (m, 1H, HAr), 7.83-7.79 (m, 1H, HAr), 7.38 (t, J = 7.8 Hz,
1H, C(O)CHC(О)), 5.06(d, J = 11.9 Hz, 1H, CHAr2), 2.39(s, 3H, 1H, HAr), 7.34-7.28 (m,2H, HAr), 7.17-7.10 (m, 2H, HAr),7.01(t, J =
CH3Ar), 2.34(d, J = 17.7 Hz, 1H, CH2), 2.17(d, J = 17.7 Hz, 1H, 8.6 Hz, 2H, HAr), 6.84 (t, J = 8.7 Hz, 2H, HAr), 5.36 (d, J = 12.0 Hz,
CH2),0.72 (s, 9H, C(CH3)3). 13С NMR (100 МHz, CDCl3): δ = 203.1 1H, C(O)CHC(О)), 5.04(d, J = 12.0 Hz, 1H, CHAr2), 2.34(d, J = 17.9
1
1
(CO), 193.4 (CO), 161.7 (d, JCF = 246 Hz, FCAr), 161.4 (d, JCF
=
Hz, 1H, CH2), 2.16(d, J = 17.9 Hz, 1H, CH2),0.73 (s, 9H, C(CH3)3).
8 | J. Name., 2012, 00, 1-3
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