(R)- and (S)-6,6'-dimethyl- and 6,6'-dimethoxy-2,2'-diiodo-1,1'-biphenyls: Versatile intermediates for the synthesis of atropisomeric diphosphine ligands

Tetrahedron Letters

Volumn 37, Issue 30, 1996, Pages 5347-5350

  Cereghetti, Marco ^a,b   Arnold, Wolf ^a   Broger, Emil A ^a   Rageot, Alain ^a  

^a F HOFFMANN LA ROCHE LTD   (Switzerland)

^b NONE   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

BIPHENYL DERIVATIVE; PHOSPHINE DERIVATIVE;

ARTICLE; DRUG SYNTHESIS; ENANTIOMER; NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0030598087     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)01090-8     Document Type: Article

References (29)

1. 1. See preceding contribution in this issue; Cereghetti, M.; Schmid, R.; Schönholzer, P.; Rageot, A.
2. 2. Heiser, B.; Broger, E.A.; Crameri, Y. Tetrahedron: Asymmetry 1991, 2, 51.
3. 3. a) Schmid, R.; Broger, E.A.; Cereghetti, M.; Crameri, Y.; Foricher, J.; Lalonde, M.; Müller, R.K.; Scalone, M.; Schoettel, G.; Zutter, U. 8th Internat. Symp. on Organometallic Chemistry Directed Towards Organic Synthesis, Santa Barbara, CA, Aug. 6-10, 1995, Pure Appl. Chem., submitted;
4. b) Nagel, U.; Krink, Th. Angew. Chem. 1993, 105, 1009; Chem. Ber. 1993, 126, 1091;
5. b) Nagel, U.; Krink, Th. Angew. Chem. 1993, 105, 1009; Chem. Ber. 1993, 126, 1091;
6. c) Nagel, U.; Bublewitz, A. Chem. Ber. 1992, 125, 1061;
7. d) Nagel, U.; Rieger, B. Organometallics 1989, 8, 1534;
8. e) Burgess, K.; Ohlmeyer, M.J.; Whitmire, K.H. Organometallics 1992, 11, 3588;
9. f) Togni, A.; Breutel, C.; Soares, M.C.; Zanetti, N.; Gerfin, T.; Gramlich, V.; Spindler, F.; Rihs, G. Inorg. Chim. Acta 1994, 222, 213;
10. g) Yoshikawa, K.; Yamamoto, N.; Murata, M.; Awano, K.; Morimoto, T.; Achiwa, K. Tetrahedron: Asymmetry 1992, 3, 13.
11. 4. Phosphorus chirality is rare due to the synthetic difficulty of controlling stereogenicity at phosphorus. For the synthesis of the P-chiral diphosphine ligand DIPAMP ephedrine was recently used as a chiral auxiliary: a) Carey, J.V.; Barker, M.D.; Brown, J.M.; Russell, M.J.H. J. Chem. Soc., Perkin Trans. 1 1993, 831;
12. b) Brown, J.M.; Carey, J.V.; Russell, M.J.H. Tetrahedron 1990, 46, 4877;
13. c) Jugé, S.; Stephan, M.; Laffitte, J.A.; Genet, J.P. Tetrahedron Lett. 1990, 31, 6357;
14. d) Jugé, S.; Stephan, M., Merdès, R.; Genet, J.P.; Halut-Desportes, S. J. Chem. Soc., Chem. Commun. 1993, 531. Factors affecting epimerization of chiral phosphines have been discussed by Mislow:
15. e) Naumann, K.; Zon, G.; Mislow, K. J. Am. Chem. Soc. 1969, 91, 7012.
16. 3g
17. 4, filtered, and evaporated. Chromatography of the residue on silica gel (hexane-toluene) gave 7.32 g (47%) (R)(S)-4a and 3.90 g (25%) (S)(S)-4a. Single crystallizations from AcOEt/MeOH afforded 3.5 g of (R)(S)-4a (100% de) and 2.3 g (S)(S)-4a (100% de according to HPLC analysis on a Chiracel OD-phase), respectively.
18. OMe: 3.56 ppm; specific rotations at 365-589 nm of all three compounds were zero.
19. 8. Miyamoto, T.K.; Matsuura, Y.; Okude, K.; Ichida, H.; Sasaki, Y. J. Organomet. Chem. 1989, 373, C8.
20. f-values of the diastereomers, notably of those with alkyl and aryl substituted phosphorus. Diphosphines with the aryl in lieu of the alkyl group in the stacking position were less polar.
21. 10. a) Schmid, R.; Cereghetti, M.; Heiser, B.; Schönhotzer, P.; Hansen, H.-J. Helv. Chim. Acta 1988, 71, 897;
22. b) Schmid, R.; Foricher, J.; Cereghetti, M.; Schönholzer, P. Helv. Chim. Acta 1991, 74, 370;
23. c) Bock, B.; Flatau, K.; Junge, H.; Kuhr, M.; Musso, H. Angew. Chem. 1971, 83, 239;
24. d) Fröhlich, R.; Musso, H. Chem. Ber. 1985, 118, 4649;
25. e) Costa, Th.; Schmidbauer, H. Chem. Ber. 1982, 115, 1367.
26. tBustacking. See a) Rebek, Jr., J. Angew. Chem. 1990, 102, 261;
27. b) Askew, B.; Ballester, P.; Buhr, C.; Jeong, K.-S.; Jones, S.; Nemeth, D.; Williams, K.; Rebek, Jr., J. J. Am. Chem. Soc. 1989, 111, 1090;
28. c) Jones, G.B.; Chapman, B.J. Synthesis 1995, 475.
29. 12. Coordinates and thermal parameters of the X-ray structures have been deposited at the Crystallographic Data Centre, Cambridge, University Chemical Lab., Cambridge CB2 1EW, England.