(3aR*,6S*,7aR*)-7a-Chloro-6-methyl-2-(4-methyl­phenyl­sulfon­yl)-2,3,3a,6,7,7a-hexa­hydro-3a,6-ep­oxy-1H-isoindole

Ersin Temel; Aydın Demircan; Gözde Beyazova; Orhan Büyükgüngör

doi:10.1107/S1600536812009658

. 2012 Mar 17;68(Pt 4):o1102–o1103. doi: 10.1107/S1600536812009658

(3aR,6S,7aR*)-7a-Chloro-6-methyl-2-(4-methylphenylsulfonyl)-2,3,3a,6,7,7a-hexahydro-3a,6-epoxy-1H-isoindole

Ersin Temel ^a,^*, Aydın Demircan ^b, Gözde Beyazova ^b, Orhan Büyükgüngör ^a

PMCID: PMC3344053 PMID: 22589962

Abstract

In the title compound, C₁₆H₁₈ClNO₃S, the six-membered ring has a boat conformation. The two five-membered rings with the bridging O atom adopt envelope conformations, whereas the N-containing five-membered ring adopts a twisted conformation. In the crystal, C—H⋯O hydrogen bonds link the molecules into a three-dimensional network.

Related literature

For background to the intramolecular Diels–Alder reaction with furan (IMDAF) as diene partner, see: Lipshutz (1986 ▶); Heiner et al. (1996 ▶); Prajapati et al. (2000 ▶); Kappe et al. (1997 ▶); Padwa et al. (1997 ▶). For our studies of the intramolecular free radical reaction of furan with a carbon side chain, see: Demircan & Parsons (1998 ▶, 2002 ▶); Demircan et al. (2006 ▶); Karaarslan et al. (2007 ▶). For our investigation of whether the protective group on nitrogen influences the cycloaddition process, see: Koşar et al. (2006 ▶); Arslan et al. (2008 ▶); Temel et al. (2011 ▶); Demircan et al. (2011 ▶). For puckering analysis, see: Cremer & Pople (1975 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₆H₁₈ClNO₃S
M _r = 339.82
Monoclinic,
a = 10.0523 (5) Å
b = 15.5135 (6) Å
c = 11.2729 (6) Å
β = 114.800 (4)°
V = 1595.84 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 296 K
0.78 × 0.72 × 0.60 mm

Data collection

Stoe IPDS 2 diffractometer
Absorption correction: integration (X-RED; Stoe & Cie, 2001 ▶) T _min = 0.746, T _max = 0.843
18547 measured reflections
3312 independent reflections
2841 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.101
S = 1.05
3312 reflections
201 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812009658/zq2155sup1.cif

e-68-o1102-sup1.cif^{(20.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812009658/zq2155Isup2.hkl

e-68-o1102-Isup2.hkl^{(159.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812009658/zq2155Isup3.cml

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
C2—H2⋯O1ⁱ	0.93	2.48	3.368 (2)	159
C5—H5⋯O3ⁱⁱ	0.93	2.62	3.539 (2)	169
C13—H13⋯O3ⁱⁱⁱ	0.93	2.67	3.601 (2)	174

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the diffractometer (purchased under grant F.279 of University Research Fund) and also the Scientific & Technological Research Council of Turkey (TÜBİTAK) for the financial support of this work (PN 107 T831).

supplementary crystallographic information

Comment

The intramolecular Diels–Alder reaction with furan (IMDAF) as diene partner provides a facile route to the synthesis of complicated multicyclic structures via oxanobornenes in synthetic organic chemistry (Lipshutz, 1986). However, in many cases, the cyclization process of IMDAF requires high pressure (Heiner et al., 1996) or the employment of Lewis acid catalysis (Prajapati et al., 2000) to proceed, the most extensively studied five-membered heterocycle for this cycloaddition is furan (Kappe et al., 1997; Padwa et al., 1997).

We have been studying intramolecular free radical reaction of furan with carbon side chain (Demircan & Parsons, 1998; 2002; Demircan et al., 2006; Karaarslan et al., 2007) and recently reported that under thermal conditions the bromofurfurylalkenes (1), with heteroatom possessed in a side chain, undergo intramolecular cycloadditions and give heterofused tricycles (2) (32–44% overall) as shown in Figure 4. We have also been researching whether the protective group on nitrogen influences cycloaddition process or not; it is noteworthy that the exchange of the protective group from tert-butoxy (Boc) group to tosyl group increases yield and accelerate the cycloaddition process. We have already reported our findings since 2005 (Koşar et al., 2006; Arslan et al., 2008; Temel et al., 2011; Demircan et al., 2011), now we report the new tricyclic structure, (3aR,6S,7aR)-7a-chloro-6-methyl-2-[(4-methylphenyl) sulfonyl]-1,2,3,6,7,7a-hexahydro-3a,6-epoxyisoindole (4), derived from the furan moiety (3) via thermal IMDAF in aqueous media with 73% yield (Figure 5).

The molecular structure of the title compound is shown in Figure 1. The title compound contains non-planar five- and six-membered rings. The six membered ring (C9—C14) has a boat conformation with puckering parameters Q = 0.944 (2) Å, θ = 89.03 (12)°, φ = 119.03 (14)°. The two five-membered rings with bridging oxygen (O3/C11/C10/C9/C14 and O3/C11—C14) adopt envelope configurations, whereas the N-containing five membered ring adopts a twisted conformation with the total puckering parameters of 0.6053 (19)°, 0.502 (2)° and 0.324 (2)°, respectively (Cremer & Pople, 1975). The crystal packing is stabilized by intermolecular C—H···O type hydrogen bonds (Table 1). Atom C13 in the reference molecule acts as a hydrogen bond donor to the bridging oxygen atom O3ⁱⁱⁱforming a C(4) chain running parallel to the c axis (iii = x, -y + 3/2, z - 1/2). Similarly, atom C5 acts as a hydrogen bond donor to the bridging oxygen atom O3ⁱⁱforming a C(9) chain running parallel to the a axis (ii = x+1, y, z). The intersection of the C(4) and C(9) chains produce R₄³(25) rings parallel to the ac plane (Fig. 2). The C2—H2···O1ⁱ (i = -x + 1, -y + 1, -z + 1) hydrogen bond produces dimeric R²₂(10) rings while the combination of C2—H2···O1ⁱ and C13—H13···O3ⁱⁱⁱ hydrogen bonds generate R⁶₆(38) rings (Fig. 3) (Bernstein et al., 1995).

Experimental

N-(2-chloroprop-2-en-1-yl)-4-methyl-N-[(5-methyl-2-furyl)methyl] benzenesulfonamide (3) (1 g, 2.94 mmol) and 50 ml water were placed in a 100 ml two neck flask, equipped with a condenser. The mixture was stirred at 371 K for 24 h and monitored by thin layer chromatography. The reaction mixture was then poured into 50 ml e thyl acetate; aqueous part was further washed with 3x50 ml ethyl acetate. The combined organic phases were washed with 50 ml brine, dried over magnesium sulfate and concentrated under reduced pressure. Subsequently, the residue was subjected to flash column chromatography to afford the title compound (4) as pale yellow crystals, re-crystallized from dichloromethane - hexane(1:4), (0.73 g, 73%).