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M . B e r nd t ,I . B rü dg a m ,H . Ha rt l * a nd H .- U . R eißig H O r opioni cac idme t h y le st e r ,C C ryst a l stru c tur eof( 2 SR , 1 ¢ RS )- 3 -(1-n a ph t h y l)- 2 -( 2 -o x o c y c lopen ty l)-p

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Crystal structure of (2SR,1 ¢ RS)-3-(1-naphthyl)-2-(2-oxocyclopentyl)- propionic acid methyl ester , C 19 H 20 O 3

M. Berndt

I

, I. Brüdgam

II

, H. Hartl*

,II

and H.-U. Reißig

I

I FreieUniversitätBerlin, InstitutfürChemie -OrganischeChemie, Takustr.3, D-14195Berlin, Germany II FreieUniversitätBerlin, InstitutfürChemie -AnorganischeChemie, Fabeckstr.34-36, D-14195Berlin, Germany

ReceivedDecember18,2003, acceptedandavailable on-lineFebruary5,2004;CCDCno. 1267/1189

Abstract

C

19

H

20

O

3

, monoclinic, P12

1

/n1 (no. 14),

a = 9.214(2) Å, b = 18.470(4) Å, c = 10.194(2) Å, b = 113.451(4)°, V = 1591.6 Å

3

, Z = 4,

R

gt

(F) = 0.042, wR

ref

(F

2

) = 0.123, T = 173 K.

Source of material

The title compound was prepared by alkylation of the lithium enolate of 1-trimethylsilanyloxy-bicyclo[3.1.0]hexane-6-carbo- xylic acid methyl ester with 1-naphthyl iodomethane, followed by ring cleavage with fluoride and HPLC separation of the diastereomers [1-4]. The diastereoisomer described here was crystallized from n-hexane/ethyl acetate; m.p. 336-337 K.

Discussion

The crystal structure proves the constitution and configuration of the title compound. It also shows a staggered conformation with respect to C12 and C15 placing the cyclopentanone carbonyl group and the naphthyl unit in fairly close proximity which is im- portant for subsequent cyclization reactions [5].

Z.Kristallogr.NCS219(2004) 47-48

47

©

byOldenbourgWissenschaftsverlag, München

Crystal: colorlessplate,size0.13×0.46×0.78 mm Wavelength: MoKaradiation (0.71073Å)

m: 0.83cm−1

Diffractometer,scan mode: BrukerSMART CCD,j/wwithDw= 0.3°

2qmax: 61.14°

N(hkl)measured,N(hkl)unique: 19463,4873 Criterion forIobs,N(hkl)gt: Iobs>2s(Iobs),3268 N(param)refined: 200

Programs: SHELXS-97[6], SHELXL-97[7], PLATON [8]

Table 1.Data collectionand handling.

H(2) 4e 0.6979 0.0034 0.0027 0.047

H(3) 4e 0.6062 −0.1139 −0.0650 0.058

H(4) 4e 0.7748 −0.2096 0.0101 0.055

H(6) 4e 1.0456 −0.2582 0.1437 0.053

H(7) 4e 1.3058 −0.2399 0.2867 0.055

H(8) 4e 1.3993 −0.1235 0.3631 0.050

H(9) 4e 1.2325 −0.0262 0.2934 0.039

H(11A) 4e 0.9092 0.0886 0.1018 0.034 H(11B) 4e 1.0836 0.0614 0.1835 0.034 H(12) 4e 1.0199 0.0328 0.3864 0.029 H(14A) 4e 0.5562 0.0669 0.3607 0.071 H(14B) 4e 0.5804 −0.0114 0.4249 0.071 H(14C) 4e 0.5299 −0.0004 0.2601 0.071 H(15) 4e 0.9946 0.1797 0.2991 0.035 H(17A) 4e 1.3353 0.2341 0.5683 0.061 H(17B) 4e 1.3127 0.1703 0.6614 0.061 H(18A) 4e 1.0873 0.2766 0.5116 0.065 H(18B) 4e 1.1172 0.2437 0.6633 0.065 H(19A) 4e 0.8804 0.1951 0.4575 0.059 H(19B) 4e 0.9899 0.1366 0.5642 0.059 Table2.Atomic coordinatesand displacementparameters(inÅ2).

Atom Site x y z Uiso

_____________

* Correspondenceauthor(e-mail:hartl@chemie.fu-berlin.de) C1

C2 C3

C5 C4 C6 C7

C8

C9 C10 C11

C12

C13

O3

O2 C14 C16 C15

O1

C17

C18

C19

(2)

48

C19H20O3

Acknowledgments.Support ofthis workby theVolkswagen-Stiftung,the ScheringAG andtheFondsderChemischenIndustrie isgratefullyacknowl- edged.

References

1. Reichelt, I.; Reissig, H.-U.: Deprotonation and Diastereoselective Alkylation of2-Siloxy-SubstitutedMethylCyclopropane-Carboxylates.

LiebigsAnn.Chem. (1984) 531-551.

2. Kunkel, E.; Reichelt, I.; Reissig, H.-U.: Ring-opening Reactions of Methyl 2-Siloxy-Cyclopropane-Carboxylates to 4-Oxoalkanoic Acid- Derivatives.LiebigsAnn.Chem. (1984) 802-819.

3. Khan, F.A.;Czerwonka, R.;Reissig, H.-U.: Pd-CatalyzedReactionsof Donor-Acceptor-SubstitutedCyclopropanesandTheirRing-OpenedDe- rivatives: Attempted Heck Cyclization and Novel One-Pot Enolate Arylations.Eur.J.Org.Chem. (2000)3607-3617.

4. Berndt, M.;Reissig, H.-U.: StereoselectiveFormation ofTri-andTetra- cyclesbySamariumDiiodide-InducedCyclizationsofNaphthylSubsti- tutedKetones.Org.Lett.6(2004) in press.

O(1) 4e 1.30010(9) 0.11556(5) 0.40524(9) 0.0280(4) 0.0418(5) 0.0500(5) −0.0019(3) 0.0172(4) −0.0061(4) O(2) 4e 0.75696(8) 0.02123(4) 0.37399(8) 0.0229(4) 0.0395(4) 0.0348(4) 0.0001(3) 0.0120(3) 0.0108(3) O(3) 4e 0.6917(1) 0.10817(5) 0.2086(1) 0.0283(4) 0.0520(5) 0.0732(7) 0.0133(4) 0.0178(4) 0.0354(5) C(1) 4e 0.9231(1) −0.02176(6) 0.1236(1) 0.0283(5) 0.0353(5) 0.0222(5) −0.0058(4) 0.0097(4) −0.0007(4) C(2) 4e 0.7679(1) −0.03526(7) 0.0354(1) 0.0314(6) 0.0511(7) 0.0295(6) −0.0056(5) 0.0057(5) 0.0015(5) C(3) 4e 0.7121(2) −0.10619(8) −0.0065(1) 0.0370(7) 0.0618(9) 0.0366(7) −0.0212(6) 0.0056(6) −0.0080(6) C(4) 4e 0.8127(2) −0.16300(7) 0.0381(1) 0.0513(8) 0.0478(7) 0.0376(7) −0.0255(6) 0.0175(6) −0.0129(6) C(5) 4e 0.9743(2) −0.15273(6) 0.1267(1) 0.0453(7) 0.0339(6) 0.0318(6) −0.0125(5) 0.0210(5) −0.0074(5) C(6) 4e 1.0818(2) −0.21144(6) 0.1726(2) 0.0631(9) 0.0289(6) 0.0515(8) −0.0072(6) 0.0345(7) −0.0083(5)

C(7) 4e 1.2369(2) −0.20072(7) 0.2583(2) 0.0546(8) 0.0360(6) 0.0569(8) 0.0090(6) 0.0325(7) 0.0022(6)

C(8) 4e 1.2933(2) −0.13043(7) 0.3040(1) 0.0351(6) 0.0441(7) 0.0473(7) 0.0043(5) 0.0179(6) −0.0004(6) C(9) 4e 1.1935(1) −0.07228(6) 0.2621(1) 0.0302(6) 0.0329(5) 0.0355(6) −0.0032(4) 0.0142(5) −0.0034(5) C(10) 4e 1.0308(1) −0.08106(6) 0.1713(1) 0.0314(5) 0.0306(5) 0.0244(5) −0.0061(4) 0.0143(4) −0.0037(4) C(11) 4e 0.9752(1) 0.05467(6) 0.1732(1) 0.0280(5) 0.0308(5) 0.0271(5) −0.0010(4) 0.0112(4) 0.0044(4) C(12) 4e 0.9636(1) 0.07052(5) 0.3173(1) 0.0213(5) 0.0230(4) 0.0286(5) 0.0025(4) 0.0097(4) 0.0053(4) C(13) 4e 0.7901(1) 0.06949(5) 0.2926(1) 0.0241(5) 0.0266(5) 0.0342(6) 0.0023(4) 0.0123(4) 0.0053(4) C(14) 4e 0.5919(1) 0.01889(8) 0.3532(2) 0.0253(6) 0.0667(9) 0.0525(8) −0.0030(6) 0.0173(6) 0.0178(7) C(15) 4e 1.0315(1) 0.14489(5) 0.3782(1) 0.0300(5) 0.0229(5) 0.0372(6) 0.0015(4) 0.0169(5) 0.0020(4) C(16) 4e 1.2113(1) 0.14820(6) 0.4453(1) 0.0311(6) 0.0283(5) 0.0336(6) −0.0049(4) 0.0136(5) 0.0010(4) C(17) 4e 1.2620(2) 0.19764(8) 0.5736(2) 0.0529(8) 0.0550(8) 0.0448(8) −0.0169(7) 0.0205(7) −0.0170(6) C(18) 4e 1.1105(2) 0.23253(7) 0.5680(2) 0.072(1) 0.0387(7) 0.068(1) −0.0155(7) 0.0446(8) −0.0221(6) C(19) 4e 0.9858(2) 0.17439(7) 0.4968(2) 0.0538(8) 0.0391(6) 0.071(1) −0.0086(6) 0.0432(8) −0.0192(6) Table3.Atomic coordinatesand displacementparameters(inÅ2).

Atom Site x y z U11 U22 U33 U12 U13 U23

5. Berndt, M.: Samariumdiiodid-induzierteCyclisierungenvonArylketonen:

MöglichkeitenundGrenzen einerneuenMethodezurDarstellung poly- cyclischerRingsysteme.Dissertation, FreieUniversitätBerlin (2003).

6. Sheldrick, G.M.: PhaseAnnealing inSHELX-90: DirectMethodsfor LargerStructures.Acta Crystallogr.A46(1990) 467-473.

7. Sheldrick, G.M.: SHELXL-97.A Program for theRefinementofCrystal Structures.UniversityofGöttingen, Germany1997.

8. Spek, A.L.: PLATON-A MultipurposeCrystallographic Tool.Utrecht University, TheNetherlands1998.

Abbildung

Table 1. Data collection and handling.

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