Methyl 2-diphenyl­phosphor­yloxy-2-aza­bicyclo­[2.2.1]hept-5-ene-3-exo-carboxyl­ate

Carlos A D Sousa; M Luísa C Vale; José E Rodríguez-Borges; Xerardo Garcia-Mera

doi:10.1107/S160053680804292X

. 2008 Dec 20;65(Pt 1):o188. doi: 10.1107/S160053680804292X

Methyl 2-diphenylphosphoryloxy-2-azabicyclo[2.2.1]hept-5-ene-3-exo-carboxylate

Carlos A D Sousa ^a,^*, M Luísa C Vale ^a, José E Rodríguez-Borges ^a, Xerardo Garcia-Mera ^b

PMCID: PMC2968096 PMID: 21581642

Abstract

In the title compound, C₂₀H₂₀NO₄P, the dihedral angle between the phenyl rings is 68.52 (7)°. In the crystal structure, the molecules are linked by a weak C—H⋯π(arene) interaction along [010] involving the phenyl CH group and the phenyl rings. There are no further significant intermolecular interactions.

Related literature

For the preparation of the precursor of the title compound, see: Sousa et al. (2008 ▶). For related literature about this type of bicyclic compound and their relevance see: Vale et al. (2006 ▶), Alves et al. (2006 ▶), Yoda et al. (1995 ▶).

Experimental

Crystal data

C₂₀H₂₀NO₄P
M _r = 369.34
Monoclinic,
a = 18.4223 (6) Å
b = 8.5522 (3) Å
c = 11.6022 (4) Å
β = 97.1810 (10)°
V = 1813.60 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 100 (2) K
0.37 × 0.34 × 0.34 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ▶) T _min = 0.871, T _max = 0.940
14828 measured reflections
3717 independent reflections
3172 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.091
S = 1.05
3717 reflections
236 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2003 ▶); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S160053680804292X/bx2188sup1.cif

e-65-0o188-sup1.cif^{(21.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680804292X/bx2188Isup2.hkl

e-65-0o188-Isup2.hkl^{(178.6KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯Cg1ⁱ	0.95	2.77	3.566 (2)	142

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Symmetry code: (i) Inline graphic . Cg1 is the centroid of the C15–C20 ring.

Acknowledgments

This work was supported by the Centro de Investigação em Química of the University of Porto. The X-ray data were collected at the Unidade de Raios X, RIAIDT, University of Santiago de Compostela. The authors thank Antonio L. Llamas-Saiz for his help and the Fundação para a Ciência e Tecnologia (FCT) and Xunta de Galicia for financial support (grants POCTI/QUI/44471/2002 and 07CSA008203-PR, respectively). CADS thanks the FCT for grant No. SFRH/BD/31526/2006.

supplementary crystallographic information

Comment

The stucture of the title compound, (I), is shown in Fig. 1. It can be seen the existence of three chiral centers at C2 (R), C5 (S) and C6 (R). In the crystalline structure, the molecules are linked by a weak C—H···π interaction, Fig. 2 [H12-πⁱ 2.77 Å, C12-H12-π 142°, C12-π 3.566 (2) Å, symmetry code: (i) 1-x,1/2+y, 1/2-z] along [010] directions. There are no further significant intermolecular interactions.

Experimental

The title compound was synthesized from the previously prepared (3exo)-2-hydroxy-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate (Sousa et al. 2008). Equimolar amounts of (3exo)-2-hydroxy-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate (0.56 g, 3.3 mmol) and diphenylpfosphinic chloride (0.63 ml, 3.3 mmol), in the presence of 1 eq. of anidrous triethylamine and and a catalytic quantity of DMAP, were let to react overnigth in dichloromethane, at room temperature under argon atmosphere. Water was added and the product was extracted with dichloromethane (3 × 15 ml). The organic layers were dried over sodium sulfate and the solvent was evaporated. The obtained product was purified by flash chromatography (eluent: dichloromethane/diethyl ether 1:1), leading to a light clear yellow oil in 80% yield. Crystals of (I) were made from a slow evaporation of a dichloromethane/hexane solution.