Toward the creation of NMR databases in chiral solvents: Bidentate chiral NMR solvents for assignment of the absolute configuration of acyclic secondary alcohols

Organic Letters

Volumn 4, Issue 3, 2002, Pages 411-414

  Kobayashi, Yoshihisa ^a   Hayashi, Nobuyuki ^a   Kishi, Yoshito ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL DERIVATIVE; SOLVENT;

ARTICLE; CHEMISTRY; CONFORMATION; FACTUAL DATABASE; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; STEREOISOMERISM;

ALCOHOLS; DATABASES, FACTUAL; MAGNETIC RESONANCE SPECTROSCOPY; MOLECULAR CONFORMATION; SOLVENTS; STEREOISOMERISM;

EID: 0037034361     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0171160     Document Type: Article

References (23)

1. For NMR databases in achiral solvents, see: (a) Kobayashi, Y.; Lee, J.; Tezuka, K.; Kishi, Y. Org. Lett. 1999, 1, 2177-2180.
2. (b) Lee, J.; Kobayashi, Y.; Tezuka, K.; Kishi, Y. Org. Lett. 1999, 1, 2181-2184.
3. (c) Kobayashi, Y.; Tan, C.-H.; Kishi, Y. Helv. Chim. Acta 2000, 83, 2562-2571.
4. (d) Kobayashi, Y.; Tan, C.-H.; Kishi, Y. Angew. Chem., Int. Ed. 2000, 39, 4279-4281.
5. (e) Tan, C.-H.; Kobayashi, Y.; Kishi, Y. Angew. Chem., Int. Ed. 2000, 39, 4282-4284.
6. (f) Kobayashi, Y.; Tan, C.-H.; Kishi, Y. J. Am. Chem. Soc. 2001, 123, 2076-2078.
7. For NMR databases in chiral solvents, see; (a) Kobayashi, Y.; Hayashi, N.; Tan, C.-H.; Kishi, Y. Org. Lett. 2001, 3, 2245-2248.
8. (b) Hayashi, N.; Kobayashi, Y.; Kishi, Y. Org. Lett. 2001, 3, 2249-2252.
9. (c) Kobayashi, Y.; Hayashi, N.; Kishi, Y. Org. Lett. 2001, 3, 2253-2255.
10. For examples, see: (a) Bambridge, K.; Begley, M. J.; Simpkins, N. S. Tetrahedron Lett. 1994, 35, 3391-3394.
11. (b) Alvaro, G.; Grepioni, F.; Savoia, D. J. Org. Chem. 1997, 62, 4180-4182.
12. (c) Grepioni, F.; Grilli, S.; Martelli, G.; Savoia, D. J. Org. Chem. 1999, 64, 3679-3683.
13. Some attempted bidentate ligands are listed in footnote 8 of ref 2c.
14. The experimental details for the synthesis of 1a-d are included in Supporting Information.
15. 6 in the coaxial inserts as an external reference (δ 29.800) and a lock-signal and with readout of NMR spectra being adjusted to 0.001 ppm/point (sw = 23980.8. fn = 524288). Half-bandwidth is 0.008 ppm.
16. 5 was found to be 0.042 and 0.020 ppm, respectively.
17. 2 column chromatography.
18. The experimental details for the synthesis and stereochemistry assignment of 9-10 and 13-14 are included in Supporting Information.
19. According to the Cahn-Ingold-Prelog convention, 9 and 11 belong to the (S)-series, whereas 10 belongs to the (R)-series.
20. The relationship between the Δδ signs and the absolute configuration of other types of alcohols, including acyclic tertiary, cyclic secondary, and diaryl alcohols, will be reported in a separate account.
21. For a case of the structural cluster spaced with a two-methylene bridge, see: Zheng, W.; DeMattei, J. A.; Wu, J.-P.; Duan, J. J.-W.; Cook, L. R.; Oinuma, H.; Kishi, Y. J. Am. Chem. Soc. 1996, 118, 7946-7968.
22. As noted in the text, the meso-1,6-diol 18 exhibited a large Δδ for the C4 carbon, instead of C3, which appeared to represent a transition from one diol-structural cluster to two independent monool-structural clusters. Assuming that this trend is held in the BMBA-p-Me solvent series, the Δδ profile of 16 appears to belong to the two independent monool-structural clusters although the C5 carbon signal is hidden under the solvent peak.
23. The sign of Δδ for the C6 carbon of 24 and 25 does not follow the prediction. However, it should be noted that the relative intensity of the C6 and C8 carbons agrees with the general trend.