The X-ray crystal structure of the title compound, as crystallized from acetonitrile-water was determined. The relative stereochemistry of the cyclohexenone ring with respect to the 8-phenylmenthyl esters was determined. The title compound crystallizes in the noncentrosymmetric space group P21, with a=8.9850(10) Å, b=15.575(3) Å, c=14.478(2) Å, β=94.61(2)°, and D calc=1.118 g cm−3 for Z=2

Bennett, Dennis W.

Chaudhury, Subhabrata

Donaldson, William

Haworth, Daniel T.

Siddiquee, Tasneem A.

English

epublications@Marquette

Marquette Universitye-Publications@MarquetteChemistry Faculty Research and Publications Chemistry, Department of8-2-2006Crystal and molecular structure ofbis(8-phenylmenthyl)2-(2-methyl-5-oxo-3-cyclohexen-1-yl)propandioate,C42H54O5• CH3CNDennis W. BennettUniversity of Wisconsin-MilwaukeeTasneem A. SiddiqueeUniversity of Wisconsin-MilwaukeeDaniel T. HaworthMarquette UniversitySubhabrata ChaudhuryMarquette UniversityWilliam DonaldsonMarquette University, william.donaldson@marquette.eduPublished version. Journal of Chemical Crystallography, Volume 36, No. 11 (August, 2006):777-780.Permalink. © 2006 Springer. Used with permission.Shareable Link. Provided by the Springer Nature SharedIt content-sharing initiative.Journal of Chemical Crystallography, Vol. 36, No. 11, November 2006 ( C© 2006)DOI: 10.1007/s10870-006-9136-yCrystal and molecular structure of bis(8-phenylmenthyl)2-(2-methyl-5-oxo-3-cyclohexen-1-yl)propandioate,C42H54O5· CH3CNDennis W. Bennett,(1) Tasneem A. Siddiquee,(1) Daniel T. Haworth,(2)Subhabrata Chaudhury,(2) and William A. Donaldson(2)∗Received December 20, 2005; accepted July 13, 2006Published Online August 1, 2006The X-ray crystal structure of the title compound, as crystallized from acetonitrile-waterwas determined. The relative stereochemistry of the cyclohexenone ring with respect tothe 8-phenylmenthyl esters was determined. The title compound crystallizes in the noncen-trosymmetric space group P21, with a = 8.9850(10) ˚A, b = 15.575(3) ˚A, c = 14.478(2) ˚A,β = 94.61(2)◦, and Dcalc = 1.118 g cm−3 for Z = 2.KEY WORDS: 2-cyclohexenone; 8-phenylmenthyl esters.As part of our research program on the ap-plication of acyclic (pentadienyl)iron(1+) cationsin synthesis,1 we discovered that the reac-tion of (3-methylpentadienyl)Fe(CO)3+ (1) withsodium malonates, followed by work up withNaHCO3, gave 4,5-disubstituted cyclohexenones2 (Scheme 1).2 This reaction presumably occursvia nucleophilic attack at an internal dienyl car-bon, on the face opposite to iron, to afford a (2-pentene-1,5-diyl)iron species 3 which undergoesCO insertion to afford the iron acyl complex 4.Reductive elimination of 4 and subsequent con-jugation of the double bond affords 2. Since thecation 1 is planar symmetric, nucleophilic attackat either C2 or C4 would give enantiomeric prod-(1) Department of Chemistry, University of Wisconsin-Milwaukee,P. O. Box 413, Milwaukee WI 53201-0413.(2) Department of Chemistry, Marquette University, Todd WehrChemistry Building, P. O. Box 1881, Milwaukee WI 53201-1881.∗ To whom correspondence should be addressed; e-mail:william.donaldson@marquette.edu.ucts. Toward this end, reaction of 1 with the anionfrom bis[(−)-8-phenylmenthyl]malonate gave thecyclohexenone (−)-2b as a single diastereomer inexcellent yield. In order to assign the stereochem-istry at C4,C5 relative to the 8-phenylmenthylesters, X-ray diffraction analysis of 2b was un-dertaken.Experimental sectionCrystallization of 2b from water–acetonitrilegave a sample which contained one moleculeof acetonitrile per cyclohexenone. A crystal(0.23 × 0.24 × 0.35 mm) was attached to a glassfiber and mounted on a Brucker P4 diffrac-tometer. The data were collected at 298 K us-ing graphite monochromatized MoKα radiation(λ= 0.71073 ˚A) and the /2 mode in the range 1.92–25.01◦. No absorption correction wasused. The structure was resolved by direct meth-ods and the data were refined by full-matrix7771074-1542/06/1100-0777/0 C© 2006 Springer Science+Business Media, Inc.778 Bennett et-alScheme 1least squares based on F2.3 A total of 4801reflections were collected (3991 independentreflections, Rint = 0.0312). The experimental crys-tallographic data is given in Table 1, and selectedTable 1. Crystal Data and Summary of Intensity Data Collectionand Structure RefinementCompound C44H57NO5CCDC Deposit No. 284152Color ColorlessCrystal dimensions (mm) 0.23 × 0.24 × 0.35Formula weight 679.91Crystal system MonoclinicSpace group P21Unit cell dimensionsa ( ˚A) 8.9850(10)b ( ˚A) 15.575(3)c ( ˚A) 14.478(2)β (◦) 94.61(2)Cell volume ( ˚A3) 2019.5(5)Z 2Density (calculated, g cm−3) 1.118Absorption coefficient (mm−1) 0.072Diffractometer Bruker P4Radiation Mo Kα (λ= 0.71073 ˚A)θ range, deg 1.92–25.01Reflections collected/unique 4801/3991 [Rint = 0.0312]Range of h, k, l − 10 to 1, − 18 to 1, − 17 to 17Structure solution Full-matrix least-squares on F2Absorption correction noneData/restraints/parameters 3991/1/451Goodness-of-fit on F2 0.965Final R indices [I > 2σ (I)] R1 = 0.0565, ωR2 = 0.1192R indices (all data) R1 = 0.1312, ωR2 = 0.1473Largest feature (e ˚A−3) 0.291 and − 0.138Temperature (K) 293(2)Table 2. Selected Bond Lengths ( ˚A) and Bond Angles (◦)C(1)–C(7) 1.551(7) C(21)–C(22) 1.327(8)C(7)–C(8) 1.545(9) C(22)–C(23) 1.482(8)C(7)–C(9) 1.510(7) C(23)–C(45) 1.518(9)C(7)–C(10) 1.582(7) C(25)–C(26) 1.510(7)C(10)–C(11) 1.520(7) C(26)–O(2) 1.189(7)C(10)–C(15) 1.514(8) C(26)–O(4) 1.344(6)C(11)–C(12) 1.510(8) C(27)–C(28) 1.532(7)C(12)–C(13) 1.534(8) C(27)–C(32) 1.512(6)C(13)–C(14) 1.515(7) C(27)–O(4) 1.478(5)C(13)–C(16) 1.513(7) C(28)–C(35) 1.559(7)C(14)–C(15) 1.503(7) C(29)–C(28) 1.544(7)C(15)–O(1) 1.467(5) C(29)–C(30) 1.521(6)C(17)–C(25) 1.530(7) C(30)–C(31) 1.499(7)C(17)–O(1) 1.321(6) C(31)–C(32) 1.531(7)C(17)–O(3) 1.201(6) C(31)–C(33) 1.530(7)C(18)–C(19) 1.508(6) C(35)–C(36) 1.549(9)C(18)–C(23) 1.524(6) C(35)–C(37) 1.540(10)C(18)–C(25) 1.546(6) C(35)–C(38) 1.538(8)C(19)–C(20) 1.506(7) C(60)–C(61) 1.409(12)C(20)–C(21) 1.443(8) C(61)–N(1) 1.093(13)C(20)–O(5) 1.213(6)C(18)–C(19)–C(20) 112.9(4) C(19)–C(18)–C(25) 114.0(4)C(19)–C(20)–C(21) 117.6(5) C(23)–C(18)–C(25) 111.7(4)C(20)–C(21)–C(22) 122.0(6) C(18)–C(23)–C(45) 114.5(5)C(21)–C(22)–C(23) 123.4(6) C(22)–C(23)–C(45) 109.8(5)C(18)–C(23)–C(22) 111.0(5) C(17)–C(25)–C(18) 111.2(4)C(19)–C(18)–C(23) 111.2(4) C(17)–C(25)–C(26) 106.1(4)C(19)–C(20)–O(5) 120.9(5) C(18)–C(25)–C(26) 111.1(4)C(21)–C(20)–O(5) 121.5(5)bond lengths and angles are given in Table 2. Thebond distances within the aromatic rings rangedfrom 1.336(8) to 1.396(9) ˚A [average = 1.373 ˚A].Results and discussionA drawing of the molecule and the crys-tallographic numbering is given in Fig. 1. Thisreveals the cis-disubstituted relative stereochem-istry about the cyclohexenone ring. Furthermore,on the basis of the known configuration of the(−)-8-phenylmenthyl group, the absolute con-figurations at C18 and C23 were found to beS and S respectively. To our knowledge, thereare no crystal structures of a 4,5-disubstituted-2-cyclohexenone. However, the bond distancesand angles within the cyclohexenone ring of 2b(Table 2) are within the average values found forother substituted cyclohexenones.4Chiral 3,4-disubstituted cyclohexenone 779Fig. 1. ORTEP view of 2b with crystallographic numbering scheme (50% probabilityellipsoids).Esters of 8-phenylmenthol have found usein diastereoselective transformations at either theα or β carbon.5 The rationale for this selectivityrelies blocking of one face of the ester by thephenyl group (see A, Fig. 2). This orientation ofthe 1-methyl-1-phenylethyl group with respectFig. 2. Conformational possibilities for the side chain of8-phenylmenthyl esters.to the cyclohexane ring is observed in a numberof crystal structures of (−)-8-phenylmenthylesters.6 Diastereoselective alkylation of bis[(−)-8-phenylmenthyl]malonates has been utilized forthe enantioselective preparation of 2-vinyl-1,1-cyclopropanedicarboxylates and 2-iodomethyl-1,1-cyclopropanedicarboxylates, as well as fordiastereoselective addition to pyridiniumcations.7 The present structure for 2b is thefirst for any bis[(−)-8-phenylmenthyl]malonate.Notably, the side chain of the pro-R ester groupadopts conformer A, while the side chain of thepro-S ester group adopts a conformer similarto B (Fig. 2). Only a few crystal structuresof 8-phenylmenthyl esters exhibit conformerB,8 while none of the crystal structures exhibitconformer C.Supplementary material Crystallographic data for the structure re-ported in this paper have been deposited with the Cambridge Crystal-lographic Data Centre as CCDC-284152. These data can be obtainedfree of charge from CCDC, 12 Union Road, Cambridge, CB2 1EZ,UK; fax: (44(0) 1223-336033; email: deposit@ccdc.cam.ac.uk.780 Bennett et-alAcknowledgmentThis material is based upon work sup-ported by the National Science Foundation (CHE-0415771).References1. (a) Li, S.; Donaldson, W.A. Synthesis 2003, 2064. (b) Yun, Y.K.;Godula, K.; Cao, Y.; Donaldson, W.A. J. Org. Chem. 2003, 68,901. (c) Lukesh, J.M.; Donaldson, W.A. Chem. Commun. 2005,110. (d) Wallock, N.J.; Donaldson, W.A. Org. Lett. 2005, 7, 2047.2. Chaudhury, S.; Donaldson, W.A. J. Am. Chem. Soc. 2006, 128,5984.3. Sheldrick, G.M., SHELX-97, Program for the Solution and Re-finement of Crystal Structures; University of Go¨ttingen: Germany,1997.4. (a) Rendle, D.F.; Trotter, J. J. Chem. Soc. Perkin Trans. 1974,2, 847. (b) Roher, D.C.; Blessing, R.H.; Daux, W.L. Acta Cryst.1979, B35, 1244. (c) Minamikawa, J.; Rice, K.C.; Jacobsen, A.E.;Brossi, A. J. Org. Chem. 1980, 45, 1901. (d) Quattropani, A.;Anderson, G.; Bernadinelli, G.; Kundig, E.P. J. Am. Chem. Soc.1997, 119, 4773. (e) Nguyen, T.M.; Selfert, R.J.; Mowrey, D.R.;Lee, D. Org. Lett. 2002, 4, 3959. (f) Singh, V.; Iyer, S.R.; Mobin,S.M. J. Org. Chem. 2005, 70, 973.5. (a) Ensley, H.E.; Beggs, M.; Gao, Y. In Encyclopedia of Reagentsfor Organic Synthesis; Paquette, L.A. Ed.; John Wiley & Sons,Ltd.: London, 1995; Vol. 3, pp. 3999–4000. (b) Oppolzer, W.Angew. Chem. Int. Ed. 1984, 23, 876. (c) Whitesell, J.K. Chem.Rev. 1992, 92, 953.6. (a) Kober, R.; Papadopoulos, K.; Miltz, W.; Enders, D.; Steglich,W. Tetrahedron 1985, 41, 1693. (b) Dyrbusch, M.; Egert, E. ActaCryst. 1992, C48, 2035. (c) Ebel, H.; Polborn, K.; Steglich, W.Eur. J. Org. Chem. 2002, 2905. (d) Takagi, R.; Hashizume, M.;Nakamura, M.; Begum, S.; Hiraga, Y.; Kojima, S.; Ohkata, K. J.Chem Soc. Perkin Trans. 2002, 1, 179. (e) Fustero, S.; Pina, B.;Salavert, E.; Navarro, A.; Ramirez de Arellano, M.C.; Fuentes,A.S. J. Org. Chem. 2002, 67, 4667. (f) Kulesza, A.; Mieczkowski,A.; Romanski, J.; Jurczak, J. Tetrahedron: Asymmetry 2003, 14,1161. (g) Muniz, K.; Nieger, M.; Mansikkamaki, H. Angew.Chem. Int. Ed. 2003, 42, 5958. (h) Kudyba, I.; Raczko, J.; Jurczak,J. J. Org. Chem. 2004, 69, 2844.7. (a) Quinkert, G.; Schmalz, H.G.; Walzer, E.; Gross, S.; Duerner,Bats, J.W. Angew. Chem. Int. Ed. 1986, 98, 732. (b) Quinkert,G.; Schmalz, H.G.; Dzierzynski, E.; Duerner, Bats, J.W. Angew.Chem. Int. Ed. 1986, 98, 1023. (c) Quinkert, G.; Schmalz,H.G.; Walzer, E.; Gross, S.; Kowalczyk-Przewloka, T.; Schier-loh, C.; Duerner, Bats, J.W. Liebig Ann. 1988, 283. (d) Inoue, T.;Kitagawa, O.; Ochiai, O.; Taguchi, T. Tetrahedron: Asymmetry1995, 6, 691. (e) Amann, R.; Arnold, K.; Spitzner, D.; Majer, Z.;Snatzke, G. Liebigs Ann. 1996, 349.8. (a) Borrione, E.; Prato, M.; Scorrano, G.; Stivanello, M.; Lucchini,V.; Valle, G. J. Chem. Soc. Perkin Trans. 1989, 1, 2245. (b) Timen,A. S.; Fischer, A.; Somfai, Chem. Commun. 2003, 1150.

Crystal and molecular structure of bis(8-phenylmenthyl) 2-(2-methyl-5-oxo-3-cyclohexen-1-yl)propandioate, C\u3csub\u3e42\u3c/sub\u3eH\u3csub\u3e54\u3c/sub\u3eO\u3csub\u3e5\u3c/sub\u3e• CH\u3csub\u3e3\u3c/sub\u3eCN

https://epublications.marquette.edu/cgi/viewcontent.cgi?article=1032&amp;context=chem_fac

Crystal and molecular structure of bis(8-phenylmenthyl) 2-(2-methyl-5-oxo-3-cyclohexen-1-yl)propandioate, C\u3csub\u3e42\u3c/sub\u3eH\u3csub\u3e54\u3c/sub\u3eO\u3csub\u3e5\u3c/sub\u3e• CH\u3csub\u3e3\u3c/sub\u3eCN

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