(2S)-2-[(2S*,5R*,6R*)-5,6-Dimeth-oxy-5,6-dimethyl-1,4-dioxan-2-yl]-1-[(S)-1,1-dimethyl-ethylsulfon-yl]aziridine.

The reaction of a sulfur ylide with a chiral non-racemic sulfinyl imine afforded the desired aziridine in excellent yield and subsequent oxidation of the sulfinyl moiety dissolved in anhydrous dichloro-methane using a 75% aqueous solution of 3-chloro-per-oxy-benzoic acid afforded the title compound, C(14)H(27)NO(6)S. The configuration of the newly formed stereogenic center at the point of attachment of the 1,4-dioxane ring to the aziridine ring is S. The configurations of the pre-existing sites 2-, 5-, and 6-positions of the 1,4-dioxane ring prior to reaction of sulfinyl imine with the sulfur ylide are S, R, and R, respectively. The C-N bond lengths of the aziridine are 1.478 (2) and 1.486 (2) Å.

Related literature

For the first synthesis of the title compound, see: Forbes et al. (2009 ▶). For the use of sulfinyl imines in the preparation of aziridines, see: Forbes et al. (2009 ▶); Chigboh et al. (2008 ▶); Morton et al. (2006 ▶). For a review on the use sulfur ylide technologies in the preparation of three-membered rings, see: McGarrigle et al. (2007 ▶). For the use of tert-butyl sulfinyl groups as stereodiscriminating groups, see: Ellman et al. (2002 ▶); Wakayama & Ellman (2009 ▶). For the use of three-carbon building blocks in the assembly of systems of medicinal significance, specifically HIV protease inhibitors, see: Izawa & Onishi (2006 ▶); Honda et al. (2004 ▶).

Experimental

Crystal data

C14H27NO6S

M = 337.43

Monoclinic,

a = 8.31483 (9) Å

b = 10.31672 (10) Å

c = 10.33015 (11) Å

β = 91.0961 (10)°

V = 885.98 (2) Å3

Z = 2

Cu Kα radiation

μ = 1.86 mm−1

T = 90 K

0.95 × 0.67 × 0.15 mm

Data collection

Oxford Diffraction SuperNova, single source at offset, Atlas diffractometer

Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2010) ▶; analytical numeric absorption correction using a multifaceted crystal model (Clark & Reid, 1995 ▶)] T min = 0.320, T max = 0.764

48647 measured reflections

3548 independent reflections

3532 reflections with I > 2σ(I)

R int = 0.082

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.104

S = 1.10

3548 reflections

206 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.25 e Å−3

Δρmin = −0.36 e Å−3

Absolute structure: Flack (1983 ▶), 1653 Friedel pairs

Flack parameter: −0.009 (13)

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810048816/hb5738sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810048816/hb5738Isup2.hkl

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

C14H27NO6S	F(000) = 364
Mr = 337.43	Dx = 1.265 Mg m−3
Monoclinic, P21	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: P 2yb	Cell parameters from 44949 reflections
a = 8.31483 (9) Å	θ = 4.3–73.3°
b = 10.31672 (10) Å	µ = 1.86 mm−1
c = 10.33015 (11) Å	T = 90 K
β = 91.0961 (10)°	Slab, colourless
V = 885.98 (2) Å3	0.95 × 0.67 × 0.15 mm
Z = 2

Oxford Diffraction SuperNova, single source at offset, Atlas diffractometer	3548 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	3532 reflections with I > 2σ(I)
mirror	Rint = 0.082
Detector resolution: 10.3613 pixels mm-1	θmax = 73.4°, θmin = 4.3°
ω scans	h = −10→10
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2010); analytical numeric absorption correction using a multifaceted crystal model (Clark & Reid, 1995)]	k = −12→12
Tmin = 0.320, Tmax = 0.764	l = −12→12
48647 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)] = 0.038	H-atom parameters constrained
wR(F2) = 0.104	w = 1/[σ2(Fo2) + (0.0774P)2 + 0.1298P] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max < 0.001
3548 reflections	Δρmax = 0.25 e Å−3
206 parameters	Δρmin = −0.35 e Å−3
1 restraint	Absolute structure: Flack (1983), 1653 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.009 (13)

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 > 2σ(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
N1	0.37564 (17)	0.58231 (13)	0.58518 (14)	0.0196 (3)
C2	0.5315 (2)	0.51956 (18)	0.61615 (16)	0.0205 (3)
H2	0.5588	0.4412	0.5639	0.025*
C3	0.5278 (2)	0.6453 (2)	0.54586 (19)	0.0284 (4)
H3A	0.5631	0.7238	0.5937	0.034*
H3B	0.5539	0.6448	0.4528	0.034*
C4	0.56425 (18)	0.51094 (17)	0.75921 (15)	0.0186 (3)
H4	0.5312	0.5935	0.8019	0.022*
O5	0.73405 (13)	0.49225 (12)	0.77640 (10)	0.0181 (2)
C6	0.7813 (2)	0.48353 (17)	0.90943 (15)	0.0190 (3)
C7	0.6875 (2)	0.37256 (17)	0.97603 (16)	0.0199 (3)
O8	0.51910 (14)	0.38873 (12)	0.95304 (11)	0.0205 (3)
C9	0.4763 (2)	0.39781 (17)	0.81885 (16)	0.0198 (3)
H9A	0.3587	0.4105	0.8087	0.024*
H9B	0.5055	0.3165	0.7741	0.024*
O10	0.73723 (16)	0.59700 (13)	0.97601 (13)	0.0243 (3)
C11	0.8058 (3)	0.7144 (2)	0.9290 (2)	0.0368 (5)
H11B	0.7977	0.7160	0.8342	0.055*
H11C	0.9192	0.7192	0.9562	0.055*
H11A	0.7476	0.7887	0.9643	0.055*
C12	0.9618 (2)	0.46183 (19)	0.90905 (17)	0.0238 (4)
H12A	1.0041	0.4623	0.9983	0.036*
H12C	1.0131	0.5312	0.8598	0.036*
H12B	0.9850	0.3780	0.8689	0.036*
O13	0.74372 (15)	0.25843 (12)	0.91606 (12)	0.0219 (3)
C14	0.6670 (2)	0.14069 (18)	0.95495 (18)	0.0261 (4)
H14C	0.6912	0.0718	0.8930	0.039*
H14A	0.5504	0.1541	0.9572	0.039*
H14B	0.7068	0.1157	1.0413	0.039*
C15	0.7090 (2)	0.3703 (2)	1.12238 (17)	0.0293 (4)
H15A	0.6786	0.4547	1.1580	0.044*
H15C	0.8219	0.3522	1.1449	0.044*
H15B	0.6406	0.3026	1.1587	0.044*
S16	0.26511 (4)	0.50297 (4)	0.47432 (3)	0.02020 (12)
O17	0.21224 (16)	0.38671 (12)	0.53743 (14)	0.0278 (3)
O18	0.35073 (16)	0.48822 (16)	0.35537 (13)	0.0323 (3)
C19	0.09768 (19)	0.61192 (18)	0.45030 (16)	0.0205 (3)
C20	0.1621 (2)	0.74360 (18)	0.40680 (19)	0.0267 (4)
H20A	0.2301	0.7807	0.4759	0.040*
H20C	0.0718	0.8021	0.3880	0.040*
H20B	0.2256	0.7323	0.3287	0.040*
C21	0.0075 (2)	0.62361 (19)	0.57736 (18)	0.0264 (4)
H21B	−0.0386	0.5393	0.5998	0.040*
H21C	−0.0790	0.6876	0.5673	0.040*
H21A	0.0822	0.6515	0.6464	0.040*
C22	−0.0086 (2)	0.5508 (2)	0.3442 (2)	0.0338 (4)
H22B	0.0512	0.5465	0.2634	0.051*
H22C	−0.1054	0.6037	0.3308	0.051*
H22A	−0.0395	0.4631	0.3704	0.051*

	U11	U22	U33	U12	U13	U23
N1	0.0192 (7)	0.0145 (7)	0.0251 (7)	−0.0006 (5)	0.0015 (5)	0.0016 (5)
C2	0.0174 (7)	0.0205 (9)	0.0239 (8)	0.0015 (6)	0.0039 (6)	0.0021 (6)
C3	0.0226 (8)	0.0290 (9)	0.0335 (9)	−0.0073 (7)	0.0004 (7)	0.0119 (8)
C4	0.0168 (7)	0.0169 (8)	0.0221 (7)	−0.0004 (7)	0.0040 (5)	0.0012 (6)
O5	0.0171 (5)	0.0175 (5)	0.0199 (5)	−0.0001 (5)	0.0038 (4)	0.0014 (5)
C6	0.0200 (7)	0.0165 (8)	0.0207 (7)	−0.0008 (6)	0.0033 (6)	−0.0021 (6)
C7	0.0217 (9)	0.0182 (8)	0.0200 (7)	−0.0015 (7)	0.0041 (6)	0.0003 (6)
O8	0.0210 (6)	0.0214 (6)	0.0192 (5)	−0.0015 (5)	0.0055 (4)	0.0001 (4)
C9	0.0194 (8)	0.0183 (8)	0.0219 (7)	−0.0021 (6)	0.0022 (6)	0.0006 (6)
O10	0.0259 (6)	0.0176 (6)	0.0297 (7)	−0.0045 (5)	0.0081 (5)	−0.0067 (5)
C11	0.0378 (12)	0.0178 (9)	0.0553 (13)	−0.0092 (8)	0.0160 (10)	−0.0113 (9)
C12	0.0195 (8)	0.0272 (9)	0.0248 (8)	−0.0014 (6)	0.0018 (6)	0.0020 (7)
O13	0.0252 (6)	0.0164 (6)	0.0244 (6)	0.0008 (5)	0.0077 (5)	0.0020 (5)
C14	0.0285 (9)	0.0189 (8)	0.0312 (9)	−0.0007 (7)	0.0089 (7)	0.0066 (7)
C15	0.0326 (9)	0.0358 (10)	0.0196 (8)	−0.0043 (8)	0.0031 (7)	0.0015 (8)
S16	0.0213 (2)	0.0156 (2)	0.0238 (2)	0.00156 (15)	0.00127 (14)	−0.00083 (14)
O17	0.0297 (7)	0.0131 (6)	0.0404 (7)	−0.0024 (5)	−0.0035 (5)	0.0021 (5)
O18	0.0329 (7)	0.0361 (8)	0.0281 (6)	0.0092 (6)	0.0054 (5)	−0.0064 (6)
C19	0.0188 (8)	0.0192 (8)	0.0235 (8)	0.0012 (6)	0.0024 (6)	0.0046 (6)
C20	0.0278 (9)	0.0205 (8)	0.0321 (9)	0.0031 (7)	0.0087 (7)	0.0081 (7)
C21	0.0237 (8)	0.0248 (9)	0.0310 (9)	0.0049 (7)	0.0093 (7)	0.0073 (7)
C22	0.0289 (9)	0.0398 (11)	0.0323 (9)	−0.0014 (8)	−0.0068 (8)	0.0023 (9)

N1—C2	1.478 (2)	C12—H12A	0.9800
N1—C3	1.486 (2)	C12—H12C	0.9800
N1—S16	1.6690 (14)	C12—H12B	0.9800
C2—C3	1.487 (3)	O13—C14	1.433 (2)
C2—C4	1.500 (2)	C14—H14C	0.9800
C2—H2	1.0000	C14—H14A	0.9800
C3—H3A	0.9900	C14—H14B	0.9800
C3—H3B	0.9900	C15—H15A	0.9800
C4—O5	1.4326 (18)	C15—H15C	0.9800
C4—C9	1.515 (2)	C15—H15B	0.9800
C4—H4	1.0000	S16—O17	1.4380 (14)
O5—C6	1.4248 (18)	S16—O18	1.4399 (14)
C6—O10	1.410 (2)	S16—C19	1.8027 (17)
C6—C12	1.518 (2)	C19—C21	1.529 (2)
C6—C7	1.553 (2)	C19—C22	1.531 (3)
C7—O13	1.414 (2)	C19—C20	1.531 (2)
C7—O8	1.425 (2)	C20—H20A	0.9800
C7—C15	1.519 (2)	C20—H20C	0.9800
O8—C9	1.428 (2)	C20—H20B	0.9800
C9—H9A	0.9900	C21—H21B	0.9800
C9—H9B	0.9900	C21—H21C	0.9800
O10—C11	1.428 (2)	C21—H21A	0.9800
C11—H11B	0.9800	C22—H22B	0.9800
C11—H11C	0.9800	C22—H22C	0.9800
C11—H11A	0.9800	C22—H22A	0.9800
C2—N1—C3	60.21 (11)	C6—C12—H12C	109.5
C2—N1—S16	113.74 (11)	H12A—C12—H12C	109.5
C3—N1—S16	119.18 (12)	C6—C12—H12B	109.5
N1—C2—C3	60.17 (11)	H12A—C12—H12B	109.5
N1—C2—C4	112.41 (14)	H12C—C12—H12B	109.5
C3—C2—C4	122.30 (16)	C7—O13—C14	115.48 (12)
N1—C2—H2	116.4	O13—C14—H14C	109.5
C3—C2—H2	116.4	O13—C14—H14A	109.5
C4—C2—H2	116.4	H14C—C14—H14A	109.5
N1—C3—C2	59.62 (11)	O13—C14—H14B	109.5
N1—C3—H3A	117.8	H14C—C14—H14B	109.5
C2—C3—H3A	117.8	H14A—C14—H14B	109.5
N1—C3—H3B	117.8	C7—C15—H15A	109.5
C2—C3—H3B	117.8	C7—C15—H15C	109.5
H3A—C3—H3B	114.9	H15A—C15—H15C	109.5
O5—C4—C2	106.87 (12)	C7—C15—H15B	109.5
O5—C4—C9	109.16 (13)	H15A—C15—H15B	109.5
C2—C4—C9	111.49 (13)	H15C—C15—H15B	109.5
O5—C4—H4	109.8	O17—S16—O18	117.33 (9)
C2—C4—H4	109.8	O17—S16—N1	105.49 (7)
C9—C4—H4	109.8	O18—S16—N1	111.26 (8)
C6—O5—C4	112.39 (11)	O17—S16—C19	109.91 (8)
O10—C6—O5	110.41 (13)	O18—S16—C19	109.97 (8)
O10—C6—C12	112.95 (14)	N1—S16—C19	101.67 (8)
O5—C6—C12	105.14 (13)	C21—C19—C22	111.19 (15)
O10—C6—C7	104.98 (13)	C21—C19—C20	111.23 (15)
O5—C6—C7	110.01 (13)	C22—C19—C20	110.84 (15)
C12—C6—C7	113.42 (14)	C21—C19—S16	108.74 (11)
O13—C7—O8	110.88 (13)	C22—C19—S16	105.99 (14)
O13—C7—C15	112.93 (15)	C20—C19—S16	108.67 (12)
O8—C7—C15	105.33 (13)	C19—C20—H20A	109.5
O13—C7—C6	104.27 (13)	C19—C20—H20C	109.5
O8—C7—C6	109.87 (14)	H20A—C20—H20C	109.5
C15—C7—C6	113.65 (15)	C19—C20—H20B	109.5
C7—O8—C9	113.28 (12)	H20A—C20—H20B	109.5
O8—C9—C4	109.40 (13)	H20C—C20—H20B	109.5
O8—C9—H9A	109.8	C19—C21—H21B	109.5
C4—C9—H9A	109.8	C19—C21—H21C	109.5
O8—C9—H9B	109.8	H21B—C21—H21C	109.5
C4—C9—H9B	109.8	C19—C21—H21A	109.5
H9A—C9—H9B	108.2	H21B—C21—H21A	109.5
C6—O10—C11	115.42 (13)	H21C—C21—H21A	109.5
O10—C11—H11B	109.5	C19—C22—H22B	109.5
O10—C11—H11C	109.5	C19—C22—H22C	109.5
H11B—C11—H11C	109.5	H22B—C22—H22C	109.5
O10—C11—H11A	109.5	C19—C22—H22A	109.5
H11B—C11—H11A	109.5	H22B—C22—H22A	109.5
H11C—C11—H11A	109.5	H22C—C22—H22A	109.5
C6—C12—H12A	109.5
S16—N1—C2—C3	111.22 (14)	C6—C7—O8—C9	55.06 (17)
C3—N1—C2—C4	115.46 (17)	C7—O8—C9—C4	−58.42 (18)
S16—N1—C2—C4	−133.32 (13)	O5—C4—C9—O8	58.54 (17)
S16—N1—C3—C2	−102.22 (14)	C2—C4—C9—O8	176.38 (13)
C4—C2—C3—N1	−99.05 (17)	O5—C6—O10—C11	−59.72 (19)
N1—C2—C4—O5	−160.31 (14)	C12—C6—O10—C11	57.7 (2)
C3—C2—C4—O5	−92.39 (19)	C7—C6—O10—C11	−178.25 (16)
N1—C2—C4—C9	80.49 (18)	O8—C7—O13—C14	−57.86 (17)
C3—C2—C4—C9	148.40 (16)	C15—C7—O13—C14	60.08 (19)
C2—C4—O5—C6	179.52 (14)	C6—C7—O13—C14	−176.06 (14)
C9—C4—O5—C6	−59.78 (17)	C2—N1—S16—O17	70.35 (13)
C4—O5—C6—O10	−58.81 (16)	C3—N1—S16—O17	138.26 (13)
C4—O5—C6—C12	179.07 (14)	C2—N1—S16—O18	−57.90 (14)
C4—O5—C6—C7	56.60 (17)	C3—N1—S16—O18	10.01 (16)
O10—C6—C7—O13	−174.97 (12)	C2—N1—S16—C19	−174.94 (12)
O5—C6—C7—O13	66.24 (15)	C3—N1—S16—C19	−107.03 (14)
C12—C6—C7—O13	−51.20 (17)	O17—S16—C19—C21	48.33 (14)
O10—C6—C7—O8	66.15 (16)	O18—S16—C19—C21	178.96 (13)
O5—C6—C7—O8	−52.65 (17)	N1—S16—C19—C21	−63.07 (13)
C12—C6—C7—O8	−170.08 (13)	O17—S16—C19—C22	−71.29 (14)
O10—C6—C7—C15	−51.58 (18)	O18—S16—C19—C22	59.34 (14)
O5—C6—C7—C15	−170.38 (14)	N1—S16—C19—C22	177.31 (12)
C12—C6—C7—C15	72.19 (19)	O17—S16—C19—C20	169.54 (12)
O13—C7—O8—C9	−59.68 (17)	O18—S16—C19—C20	−59.83 (14)
C15—C7—O8—C9	177.84 (14)	N1—S16—C19—C20	58.14 (13)