(4R)-4-(Biphenyl-4-yl)-7-chloro-1,2,3,4-tetra­hydro­quinoline

Thomas Theissmann; Michael Bolte

doi:10.1107/S160053681103830X

. 2011 Sep 30;67(Pt 10):o2747. doi: 10.1107/S160053681103830X

(4R)-4-(Biphenyl-4-yl)-7-chloro-1,2,3,4-tetrahydroquinoline

Thomas Theissmann ^a, Michael Bolte ^b,^*

PMCID: PMC3201410 PMID: 22064825

Abstract

The title compound, C₂₁H₁₈ClN, was synthesized by an enantioselective Brønsted acid-catalysed transfer hydrogenation reaction. The six-membered heterocycle adopts a half-chair conformation. It has the biphenyl residue in an axial position. The two rings of the biphenyl residue are almost coplanar [dihedral angle = 2.65 (9)°]. The crystal packing is stabilized by N—H⋯Cl hydrogen bonds, which connect the molecules into chains running along the a axis.

Related literature

For organocatalysed processes, see: Rueping, Sugiono & Schoepke (2010 ▶); Rueping, Dufour & Schoepke (2011 ▶). For Brønsted acid-catalysed transfer hydrogenations, see: Rueping et al. (2008 ▶); Rueping, Stoeckel et al. (2010 ▶). For the synthesis of the title compound, see: Rueping, Theissmann et al. (2011 ▶).

Experimental

Crystal data

C₂₁H₁₈ClN
M _r = 319.81
Orthorhombic,
a = 5.5354 (4) Å
b = 8.0039 (4) Å
c = 35.8207 (17) Å
V = 1587.03 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 173 K
0.35 × 0.21 × 0.11 mm

Data collection

STOE IPDS II two-circle-diffractometer
Absorption correction: multi-scan (MULABS; Spek, 2009 ▶; Blessing, 1995 ▶) T _min = 0.921, T _max = 0.984
18042 measured reflections
3071 independent reflections
2867 reflections with I > 2σ(I)
R _int = 0.059

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.079
S = 1.05
3071 reflections
213 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.18 e Å⁻³
Absolute structure: Flack (1983 ▶), 1240 Friedel pairs
Flack parameter: 0.01 (5)

Data collection: X-AREA (Stoe & Cie, 2001 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681103830X/lr2028sup1.cif

e-67-o2747-sup1.cif^{(19.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681103830X/lr2028Isup2.hkl

e-67-o2747-Isup2.hkl^{(150.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681103830X/lr2028Isup3.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
N1—H1⋯Cl1ⁱ	0.90 (3)	2.66 (3)	3.5466 (17)	171 (2)

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

Tetrahydroquinolines are widely distributed in nature. Due to their importance as synthetic intermediates in the preparation of pharmaceuticals, agrochemicals, and in material science, considerable effort has been made to prepare these important molecules. Recently organocatalyzed processes have found widespread applications (Rueping, Sugiono & Schoepke, 2010; Rueping, Dufour & Schoepke, 2011). In particular Brønsted acid catalyzed transfer hydrogenations have been reported to provide a series of N-heterocyclic compounds with highest enantioselectivities (Rueping et al., 2008; Rueping, Stoeckel et al., 2010). The title compound was synthesized for the first time following this methodology (Rueping, Theissmann et al., 2011) and colourless plates suitable for crystal structure determination were obtained.

The six-membered heterocycle in the title compound adopts a half chair conformation. It has the biphenyl residue in an axial position. The two rings of the biphenyl residue are almost coplanar [dihedral angle 2.65 (9)°]. The crystal packing is stabilized by N—H···Cl hydrogen bonds connecting the molecules to chains running along the a axis.

Experimental

The title compound has been synthesized as described by Rueping, Theissmann et al. (2011).