(3S,4S)-1-Benzyl­pyrrolidine-3,4-diol

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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.032
• wR factor = 0.105
• Data-to-parameter ratio = 11.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT024_ALERT_4_C Merging of Friedel Pairs is Indicated ..........          !
PLAT031_ALERT_4_C Refined Extinction Parameter within Range ......       2.91 Sigma

Alert level G
REFLT03_ALERT_4_G  ALERT: MoKa measured Friedel data cannot be used to
                   determine absolute structure in a light-atom
                   study EXCEPT under VERY special conditions.
                   It is preferred that Friedel data is merged in such cases.
           From the CIF: _diffrn_reflns_theta_max           25.10
           From the CIF: _reflns_number_total               1440
           Count of symmetry unique reflns          969
           Completeness (_total/calc)            148.61%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       471
           Fraction of Friedel pairs measured     0.486
           Are heavy atom types Z>Si present         no
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT791_ALERT_4_G The Model has Chirality at C9      (Verify) ....          S
PLAT791_ALERT_4_G The Model has Chirality at C10     (Verify) ....          S

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   5 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. 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.

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 hydrogenations (Tang & Zhang, 2003).

S2. 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.

S3. 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).

Computing details

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

	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

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) Å^3	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 monochromator	Rint = 0.000
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 F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.105	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.080P)^2] where P = (Fo^2 + 2Fc^2)/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)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

Cg2 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1^i	0.82	2.13	2.918 (2)	162
O2—H2···O1^ii	0.82	2.14	2.914 (2)	157
C10—H10···Cg2^iii	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.