(1R,2S)-[(R)-1-(2-Hy­droxy­naphthalen-1-yl)naphthalen-2-yl] 2-ethynyl­cyclo­propane-1-carboxyl­ate

Jinlong Fan; Zhaohai Qin

doi:10.1107/S1600536811011627

. 2011 May 7;67(Pt 6):o1342. doi: 10.1107/S1600536811011627

(1R,2S)-[(R)-1-(2-Hydroxynaphthalen-1-yl)naphthalen-2-yl] 2-ethynylcyclopropane-1-carboxylate

Jinlong Fan ^a, Zhaohai Qin ^a,^*

PMCID: PMC3120562 PMID: 21754737

Abstract

In the crystal structure of the title compound, C₂₆H₁₈O₃, molecules with stereochemistry (1R,2S,R), are connected by O—H⋯O hydrogen bonds, forming chains.

Related literature

The title structure is a stable cyclopropane formate ester intermediate in the synthesis of abscisic acid analogues. (1S)-(+)-Abscisic acid is an important phytohormone with many functions in higher plants including roles in seed germination, development and dormancy, regulating the stomatal movements and improving stress tolerance, see: Frey et al. (1999 ▶); Jiang & Zhang (2004 ▶). For the synthesis of cyclopropane formate ester, see: Reichelt & Martin (2006 ▶); Boche & Lohrenz (2001 ▶); Lebel et al. (2003 ▶); Molander & Etter (1987 ▶).

Experimental

Crystal data

C₂₆H₁₈O₃
M _r = 378.40
Orthorhombic,
a = 8.0376 (11) Å
b = 12.0600 (17) Å
c = 20.324 (3) Å
V = 1970.1 (5) Å³
Z = 4
Cu Kα radiation
μ = 0.66 mm⁻¹
T = 173 K
0.65 × 0.48 × 0.35 mm

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 2001 ▶) T _min = 0.673, T _max = 0.801
13939 measured reflections
3554 independent reflections
3391 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.074
S = 1.07
3554 reflections
262 parameters
H-atom parameters constrained
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.13 e Å⁻³
Absolute structure: Flack (1983 ▶), 1471 Friedel pairs
Flack parameter: −0.06 (19)

Data collection: RAPID-AUTO (Rigaku 1998 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811011627/gw2095sup1.cif

e-67-o1342-sup1.cif^{(21.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811011627/gw2095Isup2.hkl

e-67-o1342-Isup2.hkl^{(174.3KB, 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
O1—H1A⋯O3ⁱ	0.84	2.01	2.8520 (16)	177

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the Natural Science Foundation of China (No. 20972184)

supplementary crystallographic information

Comment

(1S)-(+)-Abscisic acid (ABA) is an important phytohormone with many functions in higher plants including roles in seed germination, development and dormancy, regulating the stomatal movements and improving stress tolerance (Frey et al., 1999; Jiang et al., 2004). The title structure, C₂₆H₁₈O₃, is a stable cyclopropane formate ester intermediate in the synthesis of Abscisic acid analoge. During the course of our study, we remove the protected group, trimethanesilicon, from the compound of (1R,2S)-((R)-2'-hydroxy-1,1'-binaphthyl-2-yl) 2-((trimethylsilyl)ethynyl)cyclopropanecarboxylate, to obtain the title compoud. In this paper, we reported crystal structure of the title compound.

The crystal structure is shown in Figure1. The crystal structure consists of one three-membered rings(A) and two naphthalene nucleus(B/C). The C22 is R configuration with the dihedral angles C22—C23—C24—C25 = 109.07 (51)°. The C24 is S configuration with the dihedral angles C21—C22—C24—C23 = 108.01 (53)°. The two naphthalene nucleus(B/C) is R configuration with the dihedral angles C(1)—C(10)—C(11)—C(20) = 92.85 (07)°. the compounds are connected by O1—H1A···O3i,hydrogen bonds (2.852, Symmetry code: (i) x + 1, y, z.).

Experimental

A solution of (1R,2S)-((R)-2'-hydroxy-1,1'-binaphthyl-2-yl) 2-((trimethylsilyl)ethynyl)cyclopropanecarboxylate (360 mg, 0.775 mmol) was cooled to 0 ^°C, and TBAF (1.0 M THF solution, 1.16 ml, 1.16 mmol) was added. The resulting solution was stirred for 3 h at 0^°C. Saturated NH4Cl solution was added, and the aqueous phase was extracted with Et₂O. The organic phase was washed with brine, dried over Na₂SO₄, filtered, and concentrated. The residue was purified by column chromatography on silica gel (1:1 hexane/benzene) to provide 23a (229.4 mg, 78.3%). 1H NMR (500 MHz, CDCl₃,TMS): δ 0.9566–1.1.0282 (m,1H), 1.0925 - 1.1524(m, 1H), 1.6355–1.7887 (m, 2 H), 1.9454–1.9527 (d, 1 H), 5.3893 (s, 1 H), 7.0617–7.0659(q,1 H), 7.2167–7.3231 (m, 6H), 7.4202–7.4686(q, 2 H), 7.8104–7.9397 (ddd,3H), 8.0015–8.0309(d, 1 H); 13 C NMR (75 MHz, CDCl₃): δ10.027, 14.828, 20.324, 29.639, 68.373, 80.191, 114.146, 118.643, 121.931, 123.372, 124.595, 125.744, 126.186, 126.542, 127.313, 127.910, 128.984, 130.116, 130.545, 132.182, 133.450, 133.577. The compound was redissolved in n-hexane (20 ml) and dichloromethane (5 ml), and crystals suitable for X-ray analysis were grown from slow evaporation of the solvent at room temperature.