(3S,4S)-1-Benzyl­pyrrolidine-3,4-diol

Lu, L.-H.; Sun, X.-L.; Wang, P.-A.

doi:10.1107/S1600536809055391

organic compounds

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Volume 66| Part 4| April 2010| Page o928

doi:10.1107/S1600536809055391

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(3S,4S)-1-Benzylpyrrolidine-3,4-diol

Li-Hua Lu,^a Xiao-Li Sun ^a and Ping-An Wang ^a ^*

^aDepartment of Chemistry, School of Pharmacy, Fourth Military Medical University, Changle West Road 17, 710032, Xi-An, People's Republic of China
^*Correspondence e-mail: ping_an1718@yahoo.com.cn

(Received 4 November 2009; accepted 24 December 2009; online 27 March 2010)

In the title compound, C₁₁H₁₅NO₂, the pyrrolidine ring adapts a twisted envelope conformation and the two hydroxyl groups are arranged in a trans conformation. The crystal packing is stabilized by intermolecular O—H⋯N and O—H⋯O hydrogen bonds. A weak C—H⋯π interaction also occurs.

Related literature

For the preparation of the title compound, see: Nagel et al. (1984 ); Inoguchi et al. (1990 ). The title compound is used in the preparation of the chiral phosphine ligand DEGphos, (+)-(3R,4R)-N-benzyl-3,4-bis(diphenylphosphino)pyrrolidine, (Nagel et al., 1984), an efficient ligand for Rh-catalysed asymmetric hydrogenation (Tang & Zhang, 2003 ).

Experimental

Crystal data

C₁₁H₁₅NO₂
M_r = 193.24
Monoclinic, P 2₁
a = 6.0244 (10) Å
b = 8.1033 (14) Å
c = 10.3981 (18) Å
β = 96.016 (2)°
V = 504.81 (15) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.31 × 0.27 × 0.14 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.973, T_max = 0.987
1440 measured reflections
1440 independent reflections
1348 reflections with I > 2σ(I)

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.105
S = 1.03
1440 reflections
125 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.11 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1ⁱ	0.82	2.13	2.918 (2)	162
O2—H2⋯O1ⁱⁱ	0.82	2.14	2.914 (2)	157
C10—H10⋯Cg2ⁱⁱⁱ	0.98	2.86	3.771 (2)	155
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z]$ ; (ii) x+1, y, z; (iii) x, y-1, z.

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: Mercury (Macrae et al., 2006 ) and CAMERON (Watkin et al., 1996 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809055391/jj2016sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809055391/jj2016Isup2.hkl

checkCIF report

Comment top

The title compound (+)-(3S,4S)-1-benzylpyrrolidine-3,4-diol was obtained from L-tartaric acid by condensation with benzylamine followed by reduction with NaBH₄—BF₃.Et₂O. This is used for preparation of the chiral phosphine ligand DEGphos ((+)-(3R,4R)-N-benzyl-3,4- bis(diphenylphosphino)pyrrolidine, (Nagel et al., 1984), an efficient ligand for Rh-catalyzed asymmetric hydrogenations (Tang & Zhang, 2003).

In the title compound, C₁₁H₁₅NO₂, the pyrrolidine ring adapts a twisted envelope formation. The two hydroxyl groups at C9 and C10 are arranged in a trans- conformation. The dihedral angle between the mean planes of the pyrrolidine phenyl rings is 62.4 (2)°. Crystal packing is stabilized by intermolecular O—H···N and O—H···O hydrogen bonds interactions. A weak C—H···Cg2 π ring intermolecular intereaction is also observed, where Cg2 = C1–C6.

Related literature top

For the preparation of the title compound, see: Nagel et al. (1984); Inoguchi et al. (1990). The title compound is used in the preparation of the chiral phosphine ligand DEGphos, (+)-(3R,4R)-N-benzyl-3,4- bis(diphenylphosphino)pyrrolidine, (Nagel et al., 1984), an efficient ligand for Rh-catalysed asymmetric hydrogenations (Tang & Zhang, 2003).

Experimental top

The synthesis of the title compound is described by Nagel et al. (1984). Crystals were grown from its solution in acetone; m.p. 371–373 K.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker); data reduction: SAINT (Bruker); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: Mercury (Macrae et al., 2006) and CAMERON (Watkin et al., 1996).

Figures top

	Fig. 1. The molecular structure of (I) showing displacement ellipsoids drawn at the 50% probability level. The hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. The packing of (I) viewed down the b axis. Dashed lines indicate hydrogen bonds.

(3S,4S)-1-benzylpyrrolidine-3,4-diol top

Crystal data top

C₁₁H₁₅NO₂	F(000) = 208
M_r = 193.24	D_x = 1.271 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1279 reflections
a = 6.0244 (10) Å	θ = 3.2–25.6°
b = 8.1033 (14) Å	µ = 0.09 mm⁻¹
c = 10.3981 (18) Å	T = 293 K
β = 96.016 (2)°	Block, colorless
V = 504.81 (15) Å³	0.31 × 0.27 × 0.14 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	1440 independent reflections
Radiation source: fine-focus sealed tube	1348 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.000
ϕ and ω scans	θ_max = 25.1°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −7→7
T_min = 0.973, T_max = 0.987	k = −8→9
1440 measured reflections	l = 0→12

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.080P)²] where P = (F_o² + 2F_c²)/3
1440 reflections	(Δ/σ)_max < 0.001
125 parameters	Δρ_max = 0.15 e Å⁻³
1 restraint	Δρ_min = −0.11 e Å⁻³

Crystal data top

C₁₁H₁₅NO₂	V = 504.81 (15) Å³
M_r = 193.24	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 6.0244 (10) Å	µ = 0.09 mm⁻¹
b = 8.1033 (14) Å	T = 293 K
c = 10.3981 (18) Å	0.31 × 0.27 × 0.14 mm
β = 96.016 (2)°

Data collection top

Bruker APEXII CCD diffractometer	1440 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1348 reflections with I > 2σ(I)
T_min = 0.973, T_max = 0.987	R_int = 0.000
1440 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	1 restraint
wR(F²) = 0.105	H-atom parameters constrained
S = 1.03	Δρ_max = 0.15 e Å⁻³
1440 reflections	Δρ_min = −0.11 e Å⁻³
125 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.5935 (2)	−0.00443 (18)	0.18867 (14)	0.0358 (4)
O1	0.3213 (2)	−0.36878 (18)	0.06145 (13)	0.0451 (4)
H1	0.3166	−0.4139	−0.0094	0.068*
O2	0.8566 (2)	−0.2626 (2)	0.03312 (13)	0.0556 (5)
H2	0.9802	−0.2956	0.0628	0.083*
C1	0.7231 (4)	0.3493 (3)	0.42248 (18)	0.0511 (6)
H1A	0.6080	0.3348	0.4744	0.061*
C2	0.8766 (4)	0.4734 (3)	0.4518 (2)	0.0602 (6)
H2A	0.8637	0.5423	0.5221	0.072*
C3	1.0500 (4)	0.4951 (3)	0.3760 (2)	0.0582 (6)
H3	1.1551	0.5777	0.3958	0.070*
C4	1.0660 (4)	0.3935 (3)	0.2711 (2)	0.0485 (5)
H4	1.1814	0.4084	0.2195	0.058*
C5	0.9109 (3)	0.2693 (3)	0.24219 (17)	0.0420 (5)
H5	0.9242	0.2010	0.1715	0.050*
C6	0.7361 (3)	0.2451 (3)	0.31701 (16)	0.0387 (4)
C7	0.5566 (3)	0.1179 (3)	0.28805 (19)	0.0469 (5)
H7A	0.5373	0.0596	0.3676	0.056*
H7B	0.4178	0.1750	0.2615	0.056*
C8	0.3888 (3)	−0.0952 (3)	0.14674 (19)	0.0395 (5)
H8A	0.2820	−0.0258	0.0956	0.047*
H8B	0.3203	−0.1384	0.2201	0.047*
C9	0.4714 (3)	−0.2340 (2)	0.06555 (16)	0.0359 (4)
H9	0.4813	−0.1938	−0.0226	0.043*
C10	0.7077 (3)	−0.2710 (2)	0.13021 (16)	0.0371 (4)
H10	0.7130	−0.3806	0.1702	0.045*
C11	0.7500 (3)	−0.1372 (3)	0.23333 (17)	0.0408 (5)
H11A	0.7195	−0.1779	0.3174	0.049*
H11B	0.9032	−0.0987	0.2389	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0299 (8)	0.0321 (8)	0.0458 (8)	−0.0001 (7)	0.0055 (6)	−0.0030 (6)
O1	0.0388 (8)	0.0407 (8)	0.0567 (7)	−0.0100 (6)	0.0099 (6)	−0.0062 (6)
O2	0.0317 (7)	0.0791 (12)	0.0574 (8)	0.0028 (8)	0.0111 (6)	−0.0130 (8)
C1	0.0573 (13)	0.0502 (14)	0.0466 (11)	0.0031 (11)	0.0097 (9)	−0.0049 (9)
C2	0.0732 (16)	0.0519 (15)	0.0531 (12)	0.0015 (12)	−0.0049 (11)	−0.0135 (11)
C3	0.0554 (14)	0.0422 (13)	0.0724 (13)	−0.0059 (11)	−0.0154 (11)	−0.0048 (11)
C4	0.0393 (11)	0.0412 (12)	0.0639 (11)	−0.0001 (9)	0.0010 (9)	0.0071 (10)
C5	0.0413 (11)	0.0373 (11)	0.0479 (9)	0.0021 (9)	0.0068 (8)	−0.0020 (8)
C6	0.0412 (10)	0.0329 (10)	0.0419 (8)	0.0043 (9)	0.0038 (7)	−0.0011 (8)
C7	0.0447 (12)	0.0407 (11)	0.0578 (11)	0.0001 (10)	0.0176 (10)	−0.0067 (10)
C8	0.0293 (10)	0.0364 (11)	0.0527 (10)	0.0002 (8)	0.0043 (8)	−0.0003 (8)
C9	0.0307 (9)	0.0342 (11)	0.0430 (8)	−0.0024 (8)	0.0045 (7)	0.0023 (8)
C10	0.0316 (10)	0.0351 (10)	0.0447 (9)	0.0036 (8)	0.0046 (7)	0.0017 (8)
C11	0.0374 (11)	0.0396 (11)	0.0446 (9)	0.0040 (9)	0.0001 (7)	0.0001 (8)

Geometric parameters (Å, º) top

N1—C8	1.463 (2)	C4—H4	0.9300
N1—C7	1.466 (2)	C5—C6	1.387 (3)
N1—C11	1.473 (3)	C5—H5	0.9300
O1—C9	1.416 (2)	C6—C7	1.501 (3)
O1—H1	0.8200	C7—H7A	0.9700
O2—C10	1.421 (2)	C7—H7B	0.9700
O2—H2	0.8200	C8—C9	1.521 (3)
C1—C2	1.379 (3)	C8—H8A	0.9700
C1—C6	1.393 (3)	C8—H8B	0.9700
C1—H1A	0.9300	C9—C10	1.539 (2)
C2—C3	1.384 (3)	C9—H9	0.9800
C2—H2A	0.9300	C10—C11	1.528 (3)
C3—C4	1.378 (3)	C10—H10	0.9800
C3—H3	0.9300	C11—H11A	0.9700
C4—C5	1.385 (3)	C11—H11B	0.9700

C8—N1—C7	111.39 (14)	C6—C7—H7B	108.2
C8—N1—C11	102.61 (14)	H7A—C7—H7B	107.3
C7—N1—C11	114.28 (14)	N1—C8—C9	102.85 (15)
C9—O1—H1	109.5	N1—C8—H8A	111.2
C10—O2—H2	109.5	C9—C8—H8A	111.2
C2—C1—C6	121.6 (2)	N1—C8—H8B	111.2
C2—C1—H1A	119.2	C9—C8—H8B	111.2
C6—C1—H1A	119.2	H8A—C8—H8B	109.1
C1—C2—C3	119.7 (2)	O1—C9—C8	109.99 (14)
C1—C2—H2A	120.1	O1—C9—C10	114.91 (16)
C3—C2—H2A	120.1	C8—C9—C10	104.09 (15)
C4—C3—C2	119.6 (2)	O1—C9—H9	109.2
C4—C3—H3	120.2	C8—C9—H9	109.2
C2—C3—H3	120.2	C10—C9—H9	109.2
C3—C4—C5	120.3 (2)	O2—C10—C11	113.17 (16)
C3—C4—H4	119.9	O2—C10—C9	107.72 (13)
C5—C4—H4	119.9	C11—C10—C9	104.29 (15)
C4—C5—C6	121.04 (19)	O2—C10—H10	110.5
C4—C5—H5	119.5	C11—C10—H10	110.5
C6—C5—H5	119.5	C9—C10—H10	110.5
C5—C6—C1	117.69 (19)	N1—C11—C10	104.06 (13)
C5—C6—C7	123.90 (17)	N1—C11—H11A	110.9
C1—C6—C7	118.38 (16)	C10—C11—H11A	110.9
N1—C7—C6	116.51 (14)	N1—C11—H11B	110.9
N1—C7—H7A	108.2	C10—C11—H11B	110.9
C6—C7—H7A	108.2	H11A—C11—H11B	109.0
N1—C7—H7B	108.2

C6—C1—C2—C3	−0.7 (3)	C7—N1—C8—C9	−169.66 (15)
C1—C2—C3—C4	0.7 (4)	C11—N1—C8—C9	−46.96 (17)
C2—C3—C4—C5	−0.6 (3)	N1—C8—C9—O1	155.98 (15)
C3—C4—C5—C6	0.5 (3)	N1—C8—C9—C10	32.37 (18)
C4—C5—C6—C1	−0.4 (3)	O1—C9—C10—O2	112.90 (17)
C4—C5—C6—C7	177.2 (2)	C8—C9—C10—O2	−126.76 (16)
C2—C1—C6—C5	0.5 (3)	O1—C9—C10—C11	−126.60 (16)
C2—C1—C6—C7	−177.25 (19)	C8—C9—C10—C11	−6.25 (19)
C8—N1—C7—C6	−166.25 (16)	C8—N1—C11—C10	42.96 (18)
C11—N1—C7—C6	78.0 (2)	C7—N1—C11—C10	163.69 (15)
C5—C6—C7—N1	11.1 (3)	O2—C10—C11—N1	94.90 (18)
C1—C6—C7—N1	−171.29 (17)	C9—C10—C11—N1	−21.88 (18)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.82	2.13	2.918 (2)	162
O2—H2···O1ⁱⁱ	0.82	2.14	2.914 (2)	157
C10—H10···Cg2ⁱⁱⁱ	0.98	2.86	3.771 (2)	155

Symmetry codes: (i) −x+1, y−1/2, −z; (ii) x+1, y, z; (iii) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₅NO₂
M_r	193.24
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	6.0244 (10), 8.1033 (14), 10.3981 (18)
β (°)	96.016 (2)
V (Å³)	504.81 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.31 × 0.27 × 0.14

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.973, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	1440, 1440, 1348
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.105, 1.03
No. of reflections	1440
No. of parameters	125
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.11

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), Mercury (Macrae et al., 2006) and CAMERON (Watkin et al., 1996).

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.82	2.13	2.918 (2)	162
O2—H2···O1ⁱⁱ	0.82	2.14	2.914 (2)	157
C10—H10···Cg2ⁱⁱⁱ	0.98	2.86	3.771 (2)	155

Symmetry codes: (i) −x+1, y−1/2, −z; (ii) x+1, y, z; (iii) x, y−1, z.

Acknowledgements

We thank the Natural Science Foundation of China (grant No. 20802092) for financial support.

References

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Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
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Tang, W. & Zhang, X. (2003). Chem. Rev. 103, 3029–3069. Web of Science CrossRef PubMed CAS Google Scholar
Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, Oxford, England. Google Scholar

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