(3S,4S)-1-Benzyl­pyrrolidine-3,4-diol

Abstract

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,

• a = 6.0244 (10) Å

• b = 8.1033 (14) Å

• c = 10.3981 (18) Å

• β = 96.016 (2)°

• V = 504.81 (15) ų

• 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[F ² > 2σ(F ²)] = 0.032

• wR(F ²) = 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

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 ▶).

Supplementary Material

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

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) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

The absolute structure could not be established from the dffraction data and was assigned based on L-tartaric acid the starting material.

All the H atoms were located in difference Fourier maps. However, they were constrained by riding model approximation. C—H_methyl=0.97 Å; C—H_aryl=0.93 Å; U_isoH_methyl and U_isoH_aryl are both 1.2 U _eq(C). O—H is 0.82Å with U_iso(H)=1.5U_eq(O).

Figures

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.

Crystal data

C11H15NO2	F(000) = 208
Mr = 193.24	Dx = 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

Bruker APEXII CCD diffractometer	1440 independent reflections
Radiation source: fine-focus sealed tube	1348 reflections with I > 2σ(I)
graphite	Rint = 0.0000
φ and ω scans	θmax = 25.1°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −7→7
Tmin = 0.973, Tmax = 0.987	k = −8→9
1440 measured reflections	l = 0→12

Refinement

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(Fo2) + (0.080P)2] where P = (Fo2 + 2Fc2)/3
1440 reflections	(Δ/σ)max < 0.001
125 parameters	Δρmax = 0.15 e Å−3
1 restraint	Δρmin = −0.11 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.