1450
Z. Shan et al. / Tetrahedron: Asymmetry 20 (2009) 1445–1450
654, 623. 1H NMR (CDCl3, 300 MHz): d 7.70–7.10 (m, 28H, Ar-H),
5.01 (s, 2H, C–H), 2.32 (s, 3H, Ar-C–H); 13C NMR (CDCl3,
75 MHz): d 143.8, 142.7, 141.5, 134.6, 129.2, 128.6, 128.1, 128.0,
127.3, 126.7, 125.4, 81.0, 69.6, 21.9. ESI-MS (m/z): 657 (M626+31),
561, 525, 393, 316. Calcd for C42H36B2O4: 626.
2001, 40, 92–138; (e) Seebach, D.; Beck, A. K.; Heckel, A. Essays Contemp. Chem.
2001, 283–306; (f) Abramson, S.; Bellocq, N.; Brunel, D.; Lasperas, M.; Moreau,
P. Chiral Catalyst Immob. Recy. 2000, 261–282; (g) Gawronski, J.; Gawronska, K.
Tartaric and Malic Acids in Synthesis; Wiley: New York, 1999. Chapter 12, pp
233–281; (h) Dahinden, R.; Beck, A. K.; Seebach, D.. In Encyclopedia of Reagents
for Organic Synthesis; Paquette, L. A., Ed.; Wiley: Chichester, 1995; Vol. 3, pp
2167–2170; (i) Braun, M. Angew. Chem., Int. Ed. 1996, 35, 519–522.
2. For the recent important investigations on application in asymmetric
synthesis: (a) Gordillo, R.; Dudding, T.; Anderson, C. D.; Houk, K. N. Org. Lett.
2007, 9, 501–503; (b) Akalay, D.; Duerner, G.; Bats, J. W.; Bolte, M.; Goebel, M.
W. J. Org. Chem. 2007, 72, 5618–5624; (c) Belokon’, Yu. N.; Maleev, V. I.;
Gugkaeva, Z. T.; Moskalenko, M. A.; Tsaloev, A. T.; Peregudov, A. S.; Gagieva, S.
Ch.; Lyssenko, K. A.; Khrustalev, V. N.; Grachev, A. V. Russ. Chem. Bull. 2007, 56,
1507–1514; (d) Gerard, B.; Sangji, S.; O’Leary, D. J.; Porco, J. A., Jr. J. Am. Chem.
Soc. 2006, 128, 7754–7755; (e) Zhang, X.; Du, H.; Wang, Z.; Wu, Y.; Ding, K. J.
Org. Chem. 2006, 71, 2862–2869; (f) Hilgraf, R.; Pfaltz, A. Adv. Synth. Catal. 2005,
347, 61–77; (g) Degni, S.; Strandman, S.; Laari, P.; Nuopponen, M.; Wilen, C. F.;
Tenhu, H.; Rosling, A. React. Funct. Polym. 2005, 62, 231–240; (h) Belokon, Y. N.;
Harutyunyan, S.; Vorontsov, E. V.; Peregudov, A. S.; Chrustalev, V. N.;
Kochetkov, K. A.; Pripadchev, D.; Sagyan, A. S.; Beck, A. K.; Seebach, D.
ARKIVOC 2004, 132–150; (i) Adam, W.; Alsters, P. L.; Neumann, R.; Saha-
Moeller, C. R.; Seebach, D.; Zhang, R. Org. Lett. 2003, 5, 725–728; (j) Heckel, A.;
Seebach, D. Chem. Eur. J. 2002, 8, 559–572; (k) Sellner, H.; Rheiner, P. B.;
Seebach, D. Helv. Chim. Acta 2002, 85, 352–387; (l) Sellner, H.; Karjalainen, J. K.;
Seebach, D. Chem. Eur. J. 2001, 7, 2873–2887; (m) Aoki, M.; Seebach, D. Helv.
Chim. Acta 2001, 84, 187–207.
4.2.12. (1R,6R)-5,5,10,10-Tetraphenyl-3,8-bis(3-methoxyphenyl)-
2,4,7,9-tetraoxa-3,8-diboro-bicyclo[4.4.0]decane (1R,6R)-I
Yield, 94%; mp 177–179 °C; ½a D20
¼ ꢂ17:5 (c 0.16, THF); IR (KBr,
ꢁ
cmꢂ1): 3062, 2953, 1575, 1487, 1450, 1384, 1334, 1295, 1232,
1047, 746, 701, 621. 1H NMR (CDCl3, 300 MHz): d 7.65–6.96 (m,
28H, Ar-H), 5.08 (s, 2H, C–H), 3.75 (s, 3H, O–C–H); 13C NMR (CDCl3,
75 MHz): d 159.1, 143.6, 142.6, 129.3, 129.0, 128.3, 128.1, 127.4,
126.9, 126.7, 125.5, 118.8, 117.7, 81.2, 69.7, 55.3. ESI-MS (EI, m/
z): 689 (M658++31), 573, 541, 437, 393, 365, 325, 255, 237. Calcd
for C42H36B2O6: 658.
4.2.13. (1R,6R)-5,5,10,10-Tetraphenyl-3,8-bis(1-naphthyl)-
2,4,7,9-tetraoxa-3,8-diboro-bicyclo[4.4.0]decane (1R,6R)-J
Yield, 91%; mp 241–245 °C; ½a D20
¼ þ49:5 (c 0.18, THF); IR (KBr,
ꢁ
cmꢂ1): 3059, 1713, 1575, 1508, 1450, 1384, 1309, 1252, 1210, 779,
697, 623. 1H NMR (CDCl3, 300 MHz): d 8.36–7.02 (m, 34H, Ar-H),
5.38 (s, 2H, C–H); 13C NMR (CDCl3, 75 MHz): d 143.8, 143.0,
137.1, 135.7, 134.9, 133.4, 132.0, 129.4, 128.6, 128.5, 128.4,
128.3, 127.4, 126.7, 126.3, 126.2, 125.3, 125.2, 81.7, 70.4. ESI-MS
(m/z): 729 (Mþ698+31), 717, 652, 451, 437, 409, 377, 341, 281, 255.
Calcd for C48H36B2O4: 698.
3. (a) Roush, W. R.; Hoong, L. K.; Palmer, M. A. J.; Park, J. C. J. Org. Chem. 1990, 55,
4109–4117; (b) Roush, W. R.; Adam, M. A.; Walts, A. E.; Harris, D. J. J. Am. Chem.
Soc. 1986, 108, 3422–3434; (c) Roush, W. R.; Walts, A. E.; Hoong, L. K. J. Am.
Chem. Soc. 1985, 107, 8186–8190.
4. (a) Llewellyn, D. B.; Arndtsen, B. A. Tetrahedron: Asymmetry 2005, 16, 1789–
1799; Luithle, J. E. A.; Pietruszka, J. J. Org. Chem. 2000, 65, 9194–9200; (b)
Luithle, J. E. A.; Pietruszka, J. Eur. J. Org. Chem. 2000, 2557–2562; (c) Luithle, J. E.
A.; Pietruszka, J. J. Org. Chem. 1999, 64, 8287–8297; (d) Luithle, J. E. A.;
Pietruszka, J. Liebigs Ann./Recueil. 1997, 2297–2302; (e) Nakayama, K.; Rainier, J.
D. Tetrahedron 1990, 46, 4165–4170.
5. Luithle, J. E. A.; Pietruszka, J.; Witt, A. Chem. Commun. 1998, 2651–2652.
6. Yim, H. K.; Wong, H. N. C. J. Org. Chem. 2004, 69, 2892–2895.
4.2.14. {(1R,6R)-5,5,10,10-Tetraphenyl-3,8-bis(4-acetylphenyl)-
2,4,7,9-tetraoxa-3,8-diboro-bicyclo[4.4.0]decane (1R,6R)-K
7. Chan, Y.; Eltepu, L.; Wentworth, P., Jr. Tetrahedron Lett. 2004, 45, 8285–8288.
8. (a) Eagon, S.; Kim, J.; Yan, K.; Haddenham, D.; Singaram, B. Tetrahedron Lett.
2007, 48, 9025–9029; (b) Cordes, D. B.; Kwong, T. J.; Morgan, K. A.; Singaram, B.
Tetrahedron Lett. 2006, 47, 349–351; (c) Suri, J. T.; Vu, T.; Hernandez, A.;
Congdon, J.; Singaram, B. Tetrahedron Lett. 2002, 43, 3649–3652.
9. Wallace, R. H.; Zong, K. K. J. Organomet. Chem. 1999, 581, 87–91.
10. (a) Furuta, K.; Maruyama, T.; Yamamoto, H. J. Am. Chem. Soc. 1991, 113, 1041–
1042; (b) Boldrini, G. P.; Lodi, L.; Tagliavini, E.; Trombini, C.; Umani-Ronchi, A. J.
Organomet. Chem. 1987, 336, 23–28.
11. Ishihara, K.; Gao, Q.; Yamamoto, H. J. Am. Chem. Soc. 1993, 115, 10412–10413.
12. Balavoine, G.; Crenne, N.; Manoury, E. Fr. 2638162, 1990; Chem. Abstr. 1991,
114, 6812.
13. (a) Liu, D. J. Ph.D. Dissertation, Wuhan University, Wuhan, 2003, in Chinese.;
(b) Shan, Z. X.; Zhou, Y.; Liu, D. J.; Ha, W. Z. Synth. React. Inorg. Metal-Org. Nano-
Metal Chem. 2005, 35, 275–279.
Yield, 91%; mp 295–299 °C; ½a D20
¼ þ12:6 (c 0.12, THF) IR (KBr,
ꢁ
cmꢂ1): 3024, 1686, 1632, 1384, 1329, 1268, 704, 653, 623; 1H NMR
(CDCl3, 300 MHz): d 7.93–7.30 (m, 28H, Ar-H), 5.11 (s, 2H, C–H),
2.57 (s, 6H, C–H); 13C NMR (CDCl3, 75 MHz): d 198.7, 143.3,
142.2, 139.3, 134.7, 129.4, 128.4, 128.3, 127.7, 127.5, 126.5,
125.3, 81.5, 69.8, 27.0. ESI-MS (m/z): 700 (M682+18), 699, 585,
553, 443. Calcd for C44H36B2O6: 682.
4.2.15. {(1R,6R)-5,5,10,10-Tetra(n-butyl)-3,8-diphenyl-2,4,7,9-
tetraoxa-3,8-diborobicyclo-[4.4.0]decane (1R,6R)-L
Yield, 52%; mp 240–242 °C; ½a D20
ꢁ
¼ þ10:8 (c 0.11, THF); 1H NMR
14. Liu, D. J.; Shan, Z. X.; Zhou, Y.; Qin, J. G. Helv. Chim. Acta 2004, 87, 2310–2317.
15. Zhou, Y.; Shan, Z. X. Tetrahedron 2006, 62, 5692–5696.
16. Zhou, Y. Ph.D. Dissertation, Wuhan University, Wuhan, 2007, in Chinese.
17. Zhou, Y.; Shan, Z. X.; Wang, B. S.; Xie, P. Organometallics 2006, 25, 4917–4919.
18. Zhou, Y.; Shan, Z. X. Tetrahedron Lett. 2007, 48, 3531–3534.
(CDCl3, 300 MHz): d 7.76 (d, J = 6.6 Hz, 4H, Ar-H), 7.36–7.25 (m, 6H,
Ar-H), 4.22 (s, 2H), 2.04–1.94 (m, 4H), 1.59–1.25 (m, 20H), 1.04–
0.93 (m, 12H). 13C NMR (CDCl3, 75 MHz): d 133.8, 130.5, 127.3,
77.5, 68.1, 36.2, 33.0, 25.5, 25.1, 23.2, 23.1.
19.
A representative procedure for the direct preparation of chiral 1,1,4,4-
tetrasubstituted butanetetraols (TSTOL) from enantiopure dialkyl tartrates:
1-phenylmagnesium bromide, which was prepared from Mg turnings (6.65 g,
277 mmol) and 1-bromobenzene (35 mL, ca. 251 mmol) in THF (100 mL)
according to conventional procedure, was cooled to 0 °C, followed by adding
dropwise the solution of diethyl (2S,3S)-tartrate (6.18 g, 30 mmol) in 10 mL
anhydrous THF with vigorous stirring. After complete addition, the reaction
solution was warmed to room temperature, continued to stir for one hour, and
then heated and refluxed for another 2 h, cooled to rt, 200 mL of cooled saturated
aqueous NH4Cl was added with stirring. The organic layer was separated, and the
aqueous layer extracted with diethyl ether (3 ꢃ 15 mL). The organic phases were
combined and dried over anhydrous Na2SO4. A yellow, viscous residue was
obtained after concentration of the organic solution. The residue was purified
through column chromatography on silica gel to give white crystals of (2S,3S)-
4.2.16. {(1R,6R)-5,5,10,10-Tetraphenyl-3,8-bis(4–hydroxyethylphe-
nyl)-2,4,7,9-tetraoxa-3,8-diborobicyclo[4.4.0]decane} (1R,6R)-M
Yield, 98%; mp 268–270 °C. ½a D20
ꢁ
¼ þ9:4 (c 0.5, THF); 1H NMR
(CDCl3, 300 MHz):
d 7.78 (d, J = 6.6 Hz, 4H, Ar-H), 7.60 (d,
J = 6.6 Hz, 4H, Ar-H); 7.41–7.27 (m, 24H, Ar-H), 5.04 (s, 2H, 2C–
H), 4.85 (q, J = 6.6 Hz, 2H), 1.44 (d, J = 6.0 Hz, 6H). 13C NMR (CDCl3,
75 MHz): d 149.2, 143.7, 142.6, 134.9, 129.3, 128.3, 128.2, 127.5,
126.7, 125.5, 124.9, 81.2, 70.8, 70.7, 69.7, 25.4.
Acknowledgments
1,1,4,4-tetraphenylbutanetetraol (TPTOL), 48% yield, mp 149–150 °C; ½a D25
¼
ꢁ
ꢂ156:6(c1.1, CHCl3);IR(KBr): 3437, 3058, 2916, 1598, 1492, 1447, 1062, 698;1H
NMR (CDCl3, 300 MHz): d 7.37–7.13 (m, 20H, Ar-H), 4.63 (d, 2H, J = 4.8 Hz, OH,
disappeared after adding D2O), 4.42 (d, 2H, J = 4.5 Hz, CH), 3.69 (d, 2H, J = 4.8 Hz,
OH, disappeared after adding D2O). 13C NMR (CDCl3, 75 MHz): d 143.8, 142.7,
134.6, 131.5, 129.3, 128.3, 128.2, 127.9, 127.5, 126.7, 125.5, 81.1, 69.7.
This work was supported by the National Natural Science Foun-
dation of China (20672083 and 20872115). The authors also thank
associate Professor Z.G. Shi, and L. Z. Zhu for their help.
20. The data can be obtained (CCDC 299938), free of charge, via www.ccdc.cam.
Centre, 12 Union Road, Cambridge CB2 1EZ, U.K. (fax: 44-1223-336033 or e-
mail: deposit@ccdc.cam.ac.uk).
21. The crystallographic data can be obtained (CCDC 687725), free of charge, via
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, U.K. (fax:
44-1223-336033 or e-mail: deposit@ccdc.cam.ac.uk).
References
1. For the important reviews: (a) Akiyama, T.; Itoh, J.; Fuchibe, K. Adv. Synth. Catal.
2006, 348, 999–1010; (b) Seebach, D. Abstracts, 37th Middle Atlantic Regional
Meeting of the American Chemical Society, New Brunswick, NJ, United States,
May 22–25, 2005; GENE-618.; (c) Leadbeater, N. E.; Marco, M. Chem. Rev. 2002,
102, 3217–3273; (d) Seebach, D.; Beck, A. K.; Heckel, A. Angew. Chem., Int. Ed.