5496
A. Riahi et al. / Tetrahedron 65 (2009) 5491–5496
CHFph), 10.92 (s, 1H, OH). 13C NMR (75 MHz, CDCl3):
d
¼20.6 (CH3),
(OCH2CH3), 14.1 (CH2CH3), 18.7 (CH3), 22.6 (CH2CH3), 29.3
(CH2CH2Cl), 31.9 (CH2CH2Cl), 56.2 (2ꢂOCH3), 61.0 (OCH3), 61.8
(OCH2CH3), 105.7 (2CHAr), 114.1 (CCOOC2H5), 123.9 (CCH2CH3),
126.4 (CCH2CH2Cl), 129.2 (COMeAr), 135.4 (CAr), 137.1 (COCH3), 139.2
(CCH3), 153.2 (2ꢂCOCH3), 158.3 (COH), 171.8 (CO). IR (neat, cmꢁ1):
~
33.5 (CH2CH2Cl), 42.0 (CH2CH2Cl), 51.9 (OCH3), 110.9 (CCOOMe),
115.0 (d, 2J¼21.0 Hz, CHFph), 119.7 (CHAr),123.6 (d, 4J¼4.0 Hz, CHFph),
127.8 (CAr), 128.5 (d, 2J¼18.5 Hz, CFph), 129.2 (d, 3J¼7.4 Hz, CHFph),
130.4 (d, 3J¼6.1 Hz, CHFph), 137.3 (CAr), 144.8 (CCH2CH2Cl), 159.2 (d,
~
1J¼242 Hz, CF), 160.6 (COH), 170.6 (CO). IR (neat, cmꢁ1):
n
¼2953
n
¼3004 (w), 2964 (w), 2930 (m), 1735 (m), 1676 (m), 1582 (m), 1461
(w), 2955 (w), 2854 (w), 1737 (w), 1665 (s), 1576 (w), 1494 (w), 1442
(m), 1353 (m), 1274 (w), 1239 (m), 1149 (w), 1071 (w), 908 (w), 799
(w), 757 (m), 733 (s), 535 (w). GC–MS (EI, 70 eV): m/z (%): 416 (Mþ,
37Cl, 24), 414 (Mþ, 35Cl, 74), 383 (5), 333 (100), 318 (9) 289 (15), 197
(6), 163 (13), 57 (21). HRMS (EI): calcd for C23H20O2ClFS [Mþ, 35Cl]:
414.08518, found 141.08511.
(m), 1454 (m), 1412 (m), 1237 (s), 1231 (m), 1144 (m), 1122 (s), 990
(m), 772 (m), 588 (w). GC–MS (EI, 70 eV): m/z (%)¼438 ([Mþ], 37Cl,
35), 436 ([Mþ], 35Cl, 100), 390 (31), 375 (15), 364 (32), 363 (21), 362
(96), 361 (17), 359 (32), 356 (13), 355 (47), 341 (15), 331 (11), 328
(18), 327 (19), 323 (12), 313 (16), 300 (16), 297 (28), 295 (15), 195
(32),191 (10), 165 (11), 155 (11), 149 (17), 141 (20), 139 (12), 135 (11),
133 (10), 125 (20), 123 (20), 113 (14), 111 (33), 109 (24), 107 (10), 85
(42), 83 (50), 81 (33), 79 (11), 71 (63), 69 (55), 57 (92), 55 (61), 44
(36), 43 (65), 42 (12), 41 (46), 40 (16), 39 (13). HRMS (EI): Calcd for
C23H29ClO6 ([M]þ, 35Cl): 436.16472; found: 436.164987.
3.5.5. Methyl 2-(2-chloroethyl)-5-hydroxy-30,40,50-trimethoxy-3-
methylbiphenyl-4-carboxylate (9e)
Starting with 8c (0.278 g,1.0 mmol), 5a (0.286 g,1.1 mmol), TiCl4
(0.22 mL, 2.0 mmol) and CH2Cl2 (75 mL), 9e was isolated as a yel-
lowish oil (0.205 g, 52%). 1H NMR (250 MHz, CDCl3):
d¼2.25 (s, 3H,
3.5.8. Methyl 2-(2-chloroethyl)-5-hydroxy-3-methyl-40-
nitrobiphenyl-4-carboxylate (9h)
CH3), 2.68 (t, 3J¼8.5 Hz, 2H, CH2CH2Cl), 3.22 (t, 3J¼6.8 Hz, 2H,
CH2CH2Cl), 3.68 (s, 6H, OCH3), 3.78 (s, 3H, OCH3), 3.85 (s, 3H, OCH3),
6.16 (s, 2H, CHAr), 6.72 (s, 1H, CHClph), 10.65 (s, 1H, OH). 13C NMR
Starting with 8d (0.233 g, 1.0 mmol), 5a (0.286 g, 1.1 mmol),
TiCl4 (0.22 mL, 2.0 mmol) and CH2Cl2 (75 mL), 9h was isolated as
a highly viscous oil (0.160 g, 46%). 1H NMR (250 MHz, CDCl3):
(75 MHz, CDCl3):
d
¼20.7 (CH3), 33.2 (CH2CH2Cl), 43.3 (CH2CH2Cl),
52.0 (OMeClph), 56.3 (2ꢂOMeAr), 61.0 (OCH3Ar), 106.0 (2ꢂCHAr),
112.1 (CCOOMe), 118.9 (CHClph), 126.9 (CCH2CH2Cl), 135.7 (CAr),
136.0 (CCH3), 137.1 (COMe), 148.4 (CClph), 153.2 (2ꢂCOCH3), 160.0
~
d
¼2.35 (s, 3H, CH3), 2.46 (t, 3J¼7.8 Hz, 2H, CH2CH2Cl), 3.30 (s, 3H,
OCH3), 3.41 (t, 3J¼6.2 Hz, 2H, CH2CH2Cl), 6.86 (s,1H, CHAr), 7.22, 7.28
(m, 2H, CHOMeAr), 8.16, 8.20 (m, 2H, CHOCH3Ar), 10.85 (s, 1H, OH). 13
C
(COH), 171.2 (CO). IR (Kapillar, cmꢁ1):
n
¼2998 (w), 2955 (w), 2922
NMR (75 MHz, CDCl3):
d
¼18.9 (CH3), 30.3 (CH2CH2Cl), 49.9 (OCH3),
(m), 2850 (w), 1733 (w), 1657 (m), 1585 (m), 1435 (m), 1285 (m),
1236 (s), 1206 (s), 1122 (s), 1009 (m), 727 (w), 545 (w). GC–MS (EI,
70 eV): m/z (%)¼496 ([Mþ], 37Cl, 29), 394 ([Mþ], 35Cl, 100), 364 (37Cl,
18), 363 (37Cl, 15), 362 (35Cl, 24), 361 (35Cl, 11), 328 (12), 327 (75),
313 (54), 312 (12), 295 (13), 282 (37), 267 (11) 224 (10),163 (14),156
(37), 142 (17), 134 (13), 127 (15), 83 (10). HRMS (EI): Calcd for
C20H23ClO6 ([M]þ, 35Cl): 394.11777.13342; found: 394.118590.
59.8 (CH2CH2Cl), 113.3 (CCOOMe), 117.9 (CHAr), 120.9 ð2CHNO ArÞ,
2
126.0 (CCH2CH2Cl), 127.7 ð2 ꢂ CH
Þ, 134 (CAr), 139.4 (CCH3),
NO2Ar
143.6 ðCNO ArÞ, 147.2 (CNO2), 158.2 (COH),168.6 (CO). IR (KBr, cmꢁ1):
2
~
n
¼3338 (w), 3107 (w), 2961 (w), 2882 (w), 1722 (w), 1666 (m), 1595
(m), 1514 (s), 1455 (m), 1434 (m), 1345 (s), 1269 (m), 1237 (s), 1198
(m), 1179 (m), 1129 (m), 1076 (m), 1027 (s), 1009 (s), 945 (w), 901
(w), 848 (m), 796 (m), 736 (m), 705 (m), 647 (m), 547 (m). GC–MS
(EI, 70 eV): m/z (%)¼349 ([M]þ, 5), 331 (27), 300 (35), 299 (28), 269
(16), 268 (100), 222 (55), 194 (12), 165 (25). HRMS (EI): Calcd for
C17H16ClNO5 ([M]þ): 349.07187; found: 349.071546.
3.5.6. Methyl 2-(2-chloroethyl)-5-hydroxy-30,40,50-trimethoxy-3,6-
dimethylbiphenyl-4-carboxylate (9f)
Starting with 8c (0.278 g, 1.0 mmol), 5h (0301 g, 1.1 mmol), TiCl4
(0.22 mL, 2.0 mmol) and CH2Cl2 (75 mL), 9f was isolated as a yel-
Acknowledgements
lowish oil (0.171 g, 42%). 1H NMR (250 MHz, CDCl3):
d¼1.78 (s, 3H,
CH3), 2.39 (s, 3H, CH3), 2.75 (t, 2J¼8.7 Hz, 2H, CH2CH2Cl), 3.27 (t,
2J¼6.8 Hz, 2H, CH2CH2Cl), 3.71 (s, 6H, OCH3), 3.80 (s, 3H, OCH3), 3.87
(s, 3H, OCH3), 6.17 (s, 2H, CHAr), 10.86 (s, 1H, OH). 13C NMR (75 MHz,
Financial support from the State of Mecklenburg-Vorpommern
is gratefully acknowledged.
CDCl3):
d
¼13.6 (CH3), 18.7 (CH3), 34.2 (CH2CH2Cl), 43.1 (CH2CH2Cl),
References and notes
52.3 (OMeClph), 56.2 (2ꢂOMeAr), 61.0 (OCH3Ar), 105.4 (2ꢂCHAr),
112.7 (CCOOMe), 123.2 (CCH3), 126.4 (CCH2CH2Cl), 135.8 (CAr), 135.9
(CCH3), 137.0 (COMe), 148.4 (CClph), 153.3 (2ꢂCOCH3), 158.4 (COH3),
~
1. For a review of 1,3-bis(silyloxy)-1,3-butadienes in general, see: Langer, P. Syn-
thesis 2002, 441.
2. For a review of the cyclization of 1,3-bis(silyloxy)-1,3-butadienes with oxalyl
chloride, see: Langer, P. Synlett 2006, 3369.
172.2 (CO). IR (neat, cmꢁ1):
n
¼2997 (w), 2952 (w), 2923 (m), 2850
(w),1730 (w), 1656 (m), 1580 (m), 1438 (m),1284 (m),1234 (s),1206
(s), 1123 (s), 1007 (m), 724 (w), 549 (w). GC–MS (EI, 70 eV): m/z
(%)¼410 ([Mþ], 37Cl, 29), 408 ([Mþ], 35Cl, 100), 378 (37Cl, 25), 376
3. Forareviewof thesynthesis of carbacycles by formal [3þ3]cyclizations of1,3-bis(silyl
enol ethers) with 1,3-dielectrophiles, see: Feist, H.; Langer, P. Synthesis 2007, 327.
4. Molander, G. A.; Cameron, K. O. J. Am. Chem. Soc. 1993, 1, 830.
5. Albrecht, U.; Nguyen, V. T. H.; Langer, P. J. Org. Chem. 2004, 69, 3417.
6. Reviews: (a) Jorgensen, K. A. Angew. Chem. 2000, 112, 3702; Angew. Chem., Int.
Ed. 2000, 39, 3558; (b) Danishefsky, S. J.; Bilodeau, M. T. Angew. Chem. 1996, 108,
1482; Angew. Chem., Int. Ed. 1996, 35, 1380; (c) Bednarski, M. D.; Lyssikatos, J. P.
In Comprehensive Organic Synthesis: Selectivity, Strategy and Efficiency in Modern
Organic Chemistry; Trost, B. M., Ed.; Elsevier: Amsterdam, 1991; Vol. 2, p 661; (d)
References 4 and 5 in Ghosh, A. K.; Mathivanan, P.; Cappiello, J.; Krishnan, K.
Tetrahedron: Asymmetry 1996, 7, 2165.
(
35Cl, 80), 348 (26), 341 (14), 327 (20), 309 (12), 296 (13), 281 (15),
188 (11), 148 (14), 137 (13), 127 (14), 125 (18), 123 (19), 119 (15), 111
(29), 109 (25), 97 (41), 95 (34), 91 (13), 85 (23), 83 (38), 81 (30), 71
(31), 69 (42), 57 (46), 56 (10), 55 (37), 43 (25), 41 (18). HRMS (EI):
Calcd for C21H25ClO6 ([M]þ, 35Cl): 408.13342; found: 408.133810.
3.5.7. Ethyl 2-(2-chloroethyl)-6-ethyl-5-hydroxy-30,40,50-
trimethoxy-3-methylbiphenyl-4-carboxylate (9g)
7. Hussain, I.; Yawer, M. A.; Appel, B.; Sher, M.; Mahal, A.; Villinger, A.; Langer, P.
Tetrahedron 2008, 64, 8003.
8. Chan, T.-H.; Brownbridge, P. J. Am. Chem. Soc. 1980, 102, 3534.
9. (a) Langer, P.; Bose, G. Angew. Chem., Int. Ed. 2003, 42, 4033; (b) Bose, G.; Nguyen,
V. T. H.; Ullah, E.; Lahiri, S.; Go¨rls, H.; Langer, P. J. Org. Chem. 2004, 69, 9128.
10. Wu, P.-L.; Wang, W.-S. J. Org. Chem. 1994, 59, 622.
Starting with 8c (0.278 g, 1.0 mmol), 5i (0.322 g, 1.1 mmol), TiCl4
(0.22 mL, 2.0 mmol) and CH2Cl2 (75 mL), 9g was isolated as a vis-
cous oil (0.175 g, 40%). 1H NMR (250 MHz, CDCl3):
d
¼0.92 (t,
11. CCDC-699738 (6a) and CCDC-699739 (9a) contain all crystallographic details of
Crystallographic Data Centre, 12 Union Road, GB-Cambridge CB21EZ; Fax:
3J¼5.7 Hz, 3H, CH2CH3), 1.08–1.10 (m, 3H, OCH2CH3), 2.46 (s, 3H,
CH3), 2.69 (q, 3J¼7.5 Hz, 2H, CH2CH3), 3.32 (t, 3J¼6.3 Hz, 2H,
CH2CH2Cl), 3.56 (t, 3J¼6.5 Hz, 2H, CH2CH2Cl), 3.76 (s, 6H, 2ꢂOCH3),
3.86 (s, 3H, OCH3), 4.39 (q, 3J¼7.3 Hz, 2H, OCH2CH3), 6.25 (s, 2H,
12. Reim, S.; Lau, M.; Adeel, M.; Hussain, I.; Yawer, M. A.; Riahi, M.; Ahmed, Z.;
Fischer, C.; Reinke, H.; Langer, P. Synthesis 2009, 445.
CHAr), 10.88 (s, 1H, OH). 13C NMR (75 MHz, CDCl3):
d¼13.1