(4R)-4-Benzyl-3-{(4S)-4-chloro-4-[(S)-2,2-dimethyl-1,3-dioxolan-4-yl]butano-yl}-1,3-oxazolidin-2-one.

The title compound, C(19)H(24)ClNO(5), was synthesized and subsequently employed in an Evans alkyl-ation. The purpose was to prove the absolute configuration in the projected synthesis of the side chain of (-)-Lytophilippine A. The oxazolidinone and the isopropylidene acetal rings have twisted conformations. The oxazolidinone and side-chain carbonyl groups are orientated in an anti-periplanar arrangement to minimize van der Waals repulsions. Furthermore, the Cl atom and the acetonide-protected secondary alcohol are also in an anti-periplanar arrangement with a torsion angle of 173.64 (14)°. The absolute configuration was determined and agrees with the configuration of the used chiral auxiliary.

Related literature

For background to the synthesis, see: Gille & Hiersemann (2010 ▶); Jang et al. (2011 ▶); Řezanka et al. (2004 ▶). For Evans alkyl­ation, see: Evans et al. (1981 ▶, 1982 ▶).

Experimental

Crystal data

C19H24ClNO5

M = 381.84

Monoclinic,

a = 11.7552 (9) Å

b = 5.9139 (4) Å

c = 13.8789 (11) Å

β = 109.023 (9)°

V = 912.16 (12) Å3

Z = 2

Mo Kα radiation

μ = 0.24 mm−1

T = 173 K

0.40 × 0.20 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 ▶) T min = 0.910, T max = 0.954

6562 measured reflections

3594 independent reflections

2515 reflections with I > 2s(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.047

S = 0.98

3594 reflections

237 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.21 e Å−3

Absolute structure: Flack (1983 ▶), 1198 Friedel pairs

Flack parameter: 0.11 (5)

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis n class="Disease">RED (Oxford Diffraction, 2008 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL-Plus (Sheldrick, 2008 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL-Plus.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811053840/ff2045sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811053840/ff2045Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811053840/ff2045Isup3.cml

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

C19H24ClNO5	F(000) = 404
Mr = 381.84	Dx = 1.390 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2793 reflections
a = 11.7552 (9) Å	θ = 2.8–29.0°
b = 5.9139 (4) Å	µ = 0.24 mm−1
c = 13.8789 (11) Å	T = 173 K
β = 109.023 (9)°	Block, white
V = 912.16 (12) Å3	0.40 × 0.20 × 0.20 mm
Z = 2

Oxford Diffraction Xcalibur Sapphire3 diffractometer	3594 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2515 reflections with I > 2s(I)
graphite	Rint = 0.033
Detector resolution: 16.0560 pixels mm-1	θmax = 26.0°, θmin = 2.8°
ω scans	h = −14→14
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	k = −7→7
Tmin = 0.910, Tmax = 0.954	l = −17→16
6562 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039	H-atom parameters constrained
wR(F2) = 0.047	w = 1/[σ2(Fo2) + (0.007P)2] where P = (Fo2 + 2Fc2)/3
S = 0.98	(Δ/σ)max < 0.001
3594 reflections	Δρmax = 0.22 e Å−3
237 parameters	Δρmin = −0.21 e Å−3
1 restraint	Absolute structure: Flack (1983), 1198 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.11 (5)

Experimental. CrysAlis RED (Oxford Diffraction, 2008), Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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

	x	y	z	Uiso*/Ueq
C1	0.1657 (2)	−0.3801 (4)	0.17220 (18)	0.0189 (6)
C2	0.0920 (2)	−0.2107 (4)	0.18929 (18)	0.0224 (7)
H2	0.1267	−0.0727	0.2202	0.027*
C3	−0.0317 (2)	−0.2418 (4)	0.1616 (2)	0.0290 (7)
H3	−0.0810	−0.1269	0.1750	0.035*
C4	−0.0827 (2)	−0.4398 (4)	0.11451 (19)	0.0270 (7)
H4	−0.1675	−0.4598	0.0940	0.032*
C5	−0.0110 (2)	−0.6085 (4)	0.0972 (2)	0.0285 (7)
H5	−0.0459	−0.7454	0.0653	0.034*
C6	0.1125 (2)	−0.5773 (4)	0.12673 (19)	0.0245 (7)
H6	0.1616	−0.6951	0.1153	0.029*
C7	0.30014 (18)	−0.3420 (4)	0.20129 (17)	0.0201 (6)
H7A	0.3425	−0.4887	0.2185	0.024*
H7B	0.3273	−0.2439	0.2623	0.024*
C8	0.3321 (2)	−0.2315 (4)	0.11426 (18)	0.0191 (6)
H8	0.2796	−0.0967	0.0885	0.023*
C9	0.3254 (2)	−0.3926 (4)	0.02582 (19)	0.0312 (7)
H9A	0.2762	−0.5272	0.0279	0.037*
H9B	0.2896	−0.3155	−0.0405	0.037*
C10	0.5254 (2)	−0.3120 (5)	0.10476 (17)	0.0206 (6)
C11	0.4985 (2)	0.0280 (4)	0.20304 (19)	0.0216 (6)
C12	0.6276 (2)	0.0996 (4)	0.2280 (2)	0.0244 (7)
H12A	0.6385	0.1773	0.1684	0.029*
H12B	0.6800	−0.0358	0.2430	0.029*
C13	0.6643 (2)	0.2563 (4)	0.31873 (19)	0.0220 (7)
H13A	0.6713	0.1670	0.3808	0.026*
H13B	0.5995	0.3689	0.3106	0.026*
C14	0.7817 (2)	0.3812 (4)	0.33466 (19)	0.0209 (6)
H14	0.7708	0.4861	0.2758	0.025*
C15	0.8252 (2)	0.5187 (4)	0.43295 (18)	0.0209 (6)
H15	0.9058	0.5866	0.4413	0.025*
C16	0.8292 (2)	0.3846 (4)	0.52813 (18)	0.0244 (6)
H16A	0.8405	0.2212	0.5187	0.029*
H16B	0.8949	0.4389	0.5886	0.029*
C17	0.6855 (2)	0.6563 (4)	0.50682 (18)	0.0229 (6)
C18	0.55163 (18)	0.6806 (5)	0.46026 (17)	0.0278 (6)
H18A	0.5204	0.5595	0.4104	0.042*
H18B	0.5328	0.8275	0.4261	0.042*
H18C	0.5143	0.6706	0.5138	0.042*
C19	0.7398 (2)	0.8166 (4)	0.59485 (18)	0.0272 (7)
H19A	0.7155	0.7708	0.6531	0.041*
H19B	0.7114	0.9706	0.5743	0.041*
H19C	0.8277	0.8121	0.6141	0.041*
Cl	0.90160 (5)	0.18577 (11)	0.33911 (5)	0.03519 (19)
N	0.46002 (17)	−0.1656 (3)	0.14456 (15)	0.0161 (5)
O1	0.44892 (15)	−0.4571 (3)	0.04026 (13)	0.0265 (4)
O2	0.63229 (13)	−0.3207 (3)	0.12130 (12)	0.0242 (4)
O3	0.42567 (14)	0.1337 (3)	0.22968 (13)	0.0314 (5)
O4	0.71441 (14)	0.4278 (2)	0.53829 (13)	0.0204 (4)
O5	0.73891 (12)	0.6923 (3)	0.42756 (11)	0.0231 (4)

	U11	U22	U33	U12	U13	U23
C1	0.0209 (14)	0.0224 (16)	0.0130 (15)	−0.0011 (12)	0.0049 (13)	0.0024 (11)
C2	0.0283 (16)	0.0211 (14)	0.0183 (17)	0.0020 (13)	0.0085 (15)	−0.0011 (12)
C3	0.0288 (17)	0.0318 (17)	0.0305 (19)	0.0072 (14)	0.0151 (16)	−0.0004 (14)
C4	0.0206 (16)	0.0364 (16)	0.0244 (18)	−0.0029 (14)	0.0079 (15)	0.0005 (14)
C5	0.0306 (17)	0.0216 (16)	0.0353 (19)	−0.0098 (14)	0.0132 (16)	−0.0060 (14)
C6	0.0290 (17)	0.0195 (14)	0.0296 (18)	0.0021 (13)	0.0158 (15)	0.0014 (13)
C7	0.0225 (13)	0.0186 (14)	0.0183 (15)	−0.0005 (14)	0.0054 (12)	−0.0032 (12)
C8	0.0156 (14)	0.0228 (14)	0.0176 (16)	0.0021 (11)	0.0038 (13)	−0.0029 (12)
C9	0.0176 (14)	0.0477 (19)	0.0294 (18)	−0.0047 (14)	0.0094 (15)	−0.0112 (14)
C10	0.0278 (14)	0.0202 (13)	0.0131 (14)	−0.0007 (16)	0.0058 (13)	0.0073 (14)
C11	0.0259 (17)	0.0204 (14)	0.0168 (16)	−0.0011 (13)	0.0046 (14)	0.0036 (13)
C12	0.0197 (14)	0.0233 (15)	0.0334 (18)	−0.0028 (12)	0.0132 (14)	−0.0045 (12)
C13	0.0198 (14)	0.0239 (16)	0.0230 (17)	0.0007 (12)	0.0078 (14)	−0.0014 (12)
C14	0.0198 (15)	0.0208 (14)	0.0239 (17)	0.0079 (13)	0.0097 (14)	0.0060 (13)
C15	0.0176 (15)	0.0202 (14)	0.0242 (17)	−0.0038 (12)	0.0058 (14)	−0.0033 (13)
C16	0.0222 (16)	0.0280 (15)	0.0205 (17)	−0.0031 (13)	0.0033 (14)	−0.0005 (13)
C17	0.0277 (14)	0.0224 (15)	0.0215 (16)	−0.0027 (15)	0.0122 (14)	−0.0001 (14)
C18	0.0277 (14)	0.0233 (13)	0.0337 (17)	−0.0015 (16)	0.0116 (14)	0.0011 (15)
C19	0.0309 (17)	0.0260 (15)	0.0279 (18)	−0.0057 (12)	0.0140 (16)	−0.0055 (13)
Cl	0.0234 (4)	0.0399 (4)	0.0430 (5)	0.0074 (4)	0.0119 (4)	−0.0058 (4)
N	0.0116 (12)	0.0175 (12)	0.0205 (14)	0.0006 (9)	0.0070 (11)	−0.0043 (9)
O1	0.0241 (11)	0.0301 (10)	0.0254 (12)	−0.0011 (8)	0.0083 (10)	−0.0127 (9)
O2	0.0193 (8)	0.0274 (9)	0.0273 (11)	0.0067 (10)	0.0096 (8)	−0.0029 (10)
O3	0.0252 (9)	0.0262 (11)	0.0473 (14)	−0.0023 (9)	0.0182 (10)	−0.0133 (9)
O4	0.0215 (11)	0.0197 (9)	0.0234 (11)	0.0000 (9)	0.0120 (9)	0.0040 (8)
O5	0.0296 (10)	0.0209 (9)	0.0241 (10)	0.0017 (10)	0.0158 (9)	0.0022 (10)

C1—C6	1.376 (3)	C11—C12	1.503 (3)
C1—C2	1.394 (3)	C12—C13	1.508 (3)
C1—C7	1.515 (3)	C12—H12A	0.9900
C2—C3	1.390 (3)	C12—H12B	0.9900
C2—H2	0.9500	C13—C14	1.517 (3)
C3—C4	1.379 (3)	C13—H13A	0.9900
C3—H3	0.9500	C13—H13B	0.9900
C4—C5	1.377 (3)	C14—C15	1.526 (3)
C4—H4	0.9500	C14—Cl	1.808 (2)
C5—C6	1.386 (3)	C14—H14	1.0000
C5—H5	0.9500	C15—O5	1.428 (2)
C6—H6	0.9500	C15—C16	1.528 (3)
C7—C8	1.524 (3)	C15—H15	1.0000
C7—H7A	0.9900	C16—O4	1.425 (3)
C7—H7B	0.9900	C16—H16A	0.9900
C8—N	1.476 (3)	C16—H16B	0.9900
C8—C9	1.536 (3)	C17—O4	1.426 (3)
C8—H8	1.0000	C17—O5	1.449 (2)
C9—O1	1.450 (2)	C17—C18	1.500 (3)
C9—H9A	0.9900	C17—C19	1.514 (3)
C9—H9B	0.9900	C18—H18A	0.9800
C10—O2	1.202 (2)	C18—H18B	0.9800
C10—O1	1.350 (3)	C18—H18C	0.9800
C10—N	1.386 (3)	C19—H19A	0.9800
C11—O3	1.211 (2)	C19—H19B	0.9800
C11—N	1.391 (3)	C19—H19C	0.9800
C6—C1—C2	118.2 (2)	C12—C13—C14	114.81 (19)
C6—C1—C7	121.8 (2)	C12—C13—H13A	108.6
C2—C1—C7	120.0 (2)	C14—C13—H13A	108.6
C3—C2—C1	120.7 (2)	C12—C13—H13B	108.6
C3—C2—H2	119.7	C14—C13—H13B	108.6
C1—C2—H2	119.7	H13A—C13—H13B	107.5
C4—C3—C2	119.8 (2)	C13—C14—C15	114.5 (2)
C4—C3—H3	120.1	C13—C14—Cl	110.85 (15)
C2—C3—H3	120.1	C15—C14—Cl	106.22 (17)
C5—C4—C3	120.1 (3)	C13—C14—H14	108.4
C5—C4—H4	120.0	C15—C14—H14	108.4
C3—C4—H4	120.0	Cl—C14—H14	108.4
C4—C5—C6	119.6 (2)	O5—C15—C14	108.09 (19)
C4—C5—H5	120.2	O5—C15—C16	103.84 (17)
C6—C5—H5	120.2	C14—C15—C16	113.78 (18)
C1—C6—C5	121.6 (2)	O5—C15—H15	110.3
C1—C6—H6	119.2	C14—C15—H15	110.3
C5—C6—H6	119.2	C16—C15—H15	110.3
C1—C7—C8	110.94 (19)	O4—C16—C15	103.26 (18)
C1—C7—H7A	109.5	O4—C16—H16A	111.1
C8—C7—H7A	109.5	C15—C16—H16A	111.1
C1—C7—H7B	109.5	O4—C16—H16B	111.1
C8—C7—H7B	109.5	C15—C16—H16B	111.1
H7A—C7—H7B	108.0	H16A—C16—H16B	109.1
N—C8—C7	112.25 (19)	O4—C17—O5	104.61 (18)
N—C8—C9	99.97 (18)	O4—C17—C18	109.5 (2)
C7—C8—C9	113.96 (18)	O5—C17—C18	108.19 (19)
N—C8—H8	110.1	O4—C17—C19	110.5 (2)
C7—C8—H8	110.1	O5—C17—C19	110.32 (19)
C9—C8—H8	110.1	C18—C17—C19	113.3 (2)
O1—C9—C8	105.4 (2)	C17—C18—H18A	109.5
O1—C9—H9A	110.7	C17—C18—H18B	109.5
C8—C9—H9A	110.7	H18A—C18—H18B	109.5
O1—C9—H9B	110.7	C17—C18—H18C	109.5
C8—C9—H9B	110.7	H18A—C18—H18C	109.5
H9A—C9—H9B	108.8	H18B—C18—H18C	109.5
O2—C10—O1	121.9 (3)	C17—C19—H19A	109.5
O2—C10—N	129.2 (3)	C17—C19—H19B	109.5
O1—C10—N	108.97 (19)	H19A—C19—H19B	109.5
O3—C11—N	118.3 (2)	C17—C19—H19C	109.5
O3—C11—C12	123.1 (2)	H19A—C19—H19C	109.5
N—C11—C12	118.6 (2)	H19B—C19—H19C	109.5
C11—C12—C13	110.96 (19)	C10—N—C11	129.0 (2)
C11—C12—H12A	109.4	C10—N—C8	111.57 (19)
C13—C12—H12A	109.4	C11—N—C8	119.42 (19)
C11—C12—H12B	109.4	C10—O1—C9	110.18 (18)
C13—C12—H12B	109.4	C16—O4—C17	106.18 (16)
H12A—C12—H12B	108.0	C15—O5—C17	109.33 (17)
C6—C1—C2—C3	0.4 (4)	O2—C10—N—C11	9.7 (4)
C7—C1—C2—C3	179.0 (2)	O1—C10—N—C11	−170.7 (2)
C1—C2—C3—C4	−1.5 (4)	O2—C10—N—C8	−172.6 (3)
C2—C3—C4—C5	1.5 (4)	O1—C10—N—C8	6.9 (3)
C3—C4—C5—C6	−0.4 (4)	O3—C11—N—C10	179.5 (2)
C2—C1—C6—C5	0.7 (4)	C12—C11—N—C10	0.9 (3)
C7—C1—C6—C5	−177.9 (2)	O3—C11—N—C8	2.0 (3)
C4—C5—C6—C1	−0.7 (4)	C12—C11—N—C8	−176.5 (2)
C6—C1—C7—C8	90.3 (3)	C7—C8—N—C10	104.9 (2)
C2—C1—C7—C8	−88.2 (3)	C9—C8—N—C10	−16.3 (2)
C1—C7—C8—N	172.7 (2)	C7—C8—N—C11	−77.2 (3)
C1—C7—C8—C9	−74.6 (3)	C9—C8—N—C11	161.60 (19)
N—C8—C9—O1	19.2 (2)	O2—C10—O1—C9	−173.6 (2)
C7—C8—C9—O1	−100.7 (2)	N—C10—O1—C9	6.8 (3)
O3—C11—C12—C13	21.4 (3)	C8—C9—O1—C10	−17.1 (2)
N—C11—C12—C13	−160.2 (2)	C15—C16—O4—C17	−35.9 (2)
C11—C12—C13—C14	−166.14 (19)	O5—C17—O4—C16	33.2 (2)
C12—C13—C14—C15	−173.5 (2)	C18—C17—O4—C16	148.95 (19)
C12—C13—C14—Cl	−53.4 (2)	C19—C17—O4—C16	−85.6 (2)
C13—C14—C15—O5	−63.7 (2)	C14—C15—O5—C17	116.1 (2)
Cl—C14—C15—O5	173.64 (14)	C16—C15—O5—C17	−5.0 (2)
C13—C14—C15—C16	51.1 (3)	O4—C17—O5—C15	−16.6 (2)
Cl—C14—C15—C16	−71.6 (2)	C18—C17—O5—C15	−133.4 (2)
O5—C15—C16—O4	24.8 (2)	C19—C17—O5—C15	102.2 (2)
C14—C15—C16—O4	−92.5 (2)