The title compound, C22H24O2, has been obtained by a Grignard reaction of (1S, 4R)-methyl 7,7-dimethyl-2-oxo-bicyclo[2.2.1]heptane-1-carboxylate with phenylmagnesium bromide. Intramolecular hydrogen bonding is observed between the carbonyl group and the hydroxy group

Gao, Y. X.

Tang, G.

Zhao, Y. F.

唐果

赵玉芬

English

Xiamen University Institutional Repository

organic papersActa Cryst. (2006). E62, o4521–o4522 doi:10.1107/S1600536806037287 Gao et al.  C22H24O2 o4521Acta Crystallographica Section EStructure ReportsOnlineISSN 1600-5368(1R,4R)-1-(Hydroxydiphenylmethyl)-7,7-di-methylbicyclo[2.2.1]heptan-2-oneYu-Xing Gao, Guo Tang* andYu-Fen ZhaoDepartment of Chemistry, The Key Laboratoryfor Chemical Biology of Fujian Province, Collegeof Chemistry and Chemical Engineering, XiamenUniversity, Xiamen 361005, People’s Republicof ChinaCorrespondence e-mail: t12g21@xmu.edu.cnKey indicatorsSingle-crystal X-ray studyT = 273 KMean (C–C) = 0.004 A˚R factor = 0.052wR factor = 0.150Data-to-parameter ratio = 8.8For details of how these key indicators wereautomatically derived from the article, seehttp://journals.iucr.org/e.Received 13 September 2006Accepted 13 September 2006# 2006 International Union of CrystallographyAll rights reservedThe title compound, C22H24O2, has been obtained by aGrignard reaction of (1S,4R)-methyl 7,7-dimethyl-2-oxo-bicyclo[2.2.1]heptane-1-carboxylate with phenylmagnesiumbromide. Intramolecular hydrogen bonding is observedbetween the carbonyl group and the hydroxy group.CommentThe title compound, (I), is an important intermediate in thesynthesis of exo-10,10-diphenyl-2,10-camphanediol, which iswidely used in asymmetric reduction as a chiral auxiliary(Chen et al., 1999). The molecular structure of (I) is shown inFig. 1. Bond lengths and angles in (I) are in agreement withthose reported for similar compounds (Chen et al., 2006). Thedihedral angle between the phenyl planes is 72.10 (6).Intramolecular hydrogen bonding is observed betweencarbonyl groups and hydroxy groups; O2—H2A = 0.82 A˚,H2A  O1 = 2.02 A˚, O2  O1 = 2.722 (3) A˚ and O2—H2A  O1 = 143.ExperimentalTo a precooled solution of (1S,4R)-methyl 7,7-dimethyl-2-oxo-bicyclo[2.2.1]heptane-1-carboxylate (0.78 g, 4 mmol) in dry tetra-hydrofuran (30 ml) at 273 K was added dropwise a 3 M solution ofphenylmagnesium bromide (6.8 ml, 20 mmol) in tetrahydrofuran.The cooling bath was removed and the mixture warmed to 308 K for10 h. The reaction was quenched with a saturated NH4Cl solution(16 ml) and extracted with ethyl acetate. The organic layer waswashed with brine, dried over anhydrous MgSO4, concentrated undervacuum and the crude product was purified by column chromato-graphy (petroleum ether–ethyl acetate, 30:1) to give the titlecompound as a white solid in 58% yield. Single crystals of (I) wereobtained by slow evaporation of a petroleum ether–ethyl acetatesolution (15:1 v/v).Crystal dataC22H24O2Mr = 320.41Orthorhombic, P212121a = 9.168 (2) A˚b = 10.053 (2) A˚c = 18.405 (4) A˚V = 1696.3 (6) A˚3Z = 4Dx = 1.255 Mg m3Mo K radiation = 0.08 mm1T = 273 (2) KChunk, colorless0.65  0.56  0.41 mmData collectionBruker APEX area-detectordiffractometer’ and ! scansAbsorption correction: none9220 measured reflections1912 independent reflections1848 reflections with I > 2(I)Rint = 0.021max = 26.0RefinementRefinement on F 2R[F 2 > 2(F 2)] = 0.052wR(F 2) = 0.150S = 1.191912 reflections217 parametersH-atom parameters constrainedw = 1/[2(Fo2) + (0.0967P)2+ 0.1778P]where P = (Fo2 + 2Fc2)/3(/)max < 0.001max = 0.20 e A˚3min = 0.18 e A˚3Methyl H atoms were placed in calculated positions, with C—H =0.96 A˚ and Uiso(H) = 1.5Ueq(C). Other H atoms were placed inidealized positions, with C—H = 0.93 (aromatic), 0.98 (methine),0.97 A˚ (methylene) and O—H = 0.82 A˚, and refined in riding mode,with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O). In the absence of significantanomalous scattering effects, Friedel pairs were merged; the absoluteconfiguration of (I) was assigned assuming that the absolute config-uration of the starting material was retained during the synthesis.Data collection: SMART (Bruker, 2001); cell refinement: SAINT(Bruker, 2001); data reduction: SAINT; program(s) used to solvestructure: SHELXS97 (Sheldrick, 1997); program(s) used to refinestructure: SHELXL97 (Sheldrick, 1997); molecular graphics:ORTEP-3 for Windows (Farrugia, 1997); software used to preparematerial for publication: SHELXL97.The authors thank the Key (Key grant) Project of theChinese Ministry of Education (No. 104201) and the NaturalScience Foundation of Fujian Province of China (No.C0310002) for supporting this work. We also thank Mr R.-B.Huang for technical assistance.ReferencesBruker (2001). SAINT (Version 6.22), SMART (Version 5.625) and SADABS(Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.Chen, C.-J., Chu, Y.-Y., Liao, Y.-Y., Tsai, Z.-H., Wang, C.-C. & Chen, K. (1999).Tetrahedron Lett. 40, 1141–1144.Chen, W.-Z., Zeng, Q.-L., Fang, H., Gao, Y.-X. & Zhao, Y.-F. (2006). ActaCryst. E62, o869–o870.Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University ofGo¨ttingen, Germany.organic paperso4522 Gao et al.  C22H24O2 Acta Cryst. (2006). E62, o4521–o4522Figure 1The molecular structure of (I), with 50% probability displacementellipsoids (arbitrary spheres for H atoms).

(1R,4R)-1-(hydroxydiphenylmethyl)-7,7-dimethylbicyclo [2.2.1] heptan-2-one

https://dspace.xmu.edu.cn/bitstream/handle/2288/88643/%281R%2c4R%29-1-%28hydroxydiphenylmethyl%29-7%2c7-dimethylbicyclo%20%5b2.2.1%5d%20heptan-2-one.pdf?sequence=1&isAllowed=y

(1R,4R)-1-(hydroxydiphenylmethyl)-7,7-dimethylbicyclo [2.2.1] heptan-2-one

Abstract

Similar works

Full text

Available Versions

Xiamen University Institutional Repository