(Z,1S,10aR)-(-)-Menthyl 1-hy-droxy-1,2,3,5,6,7,10,10a-octa-hydro-pyrrolo-[1,2-a]azocine-10a-carboxyl-ate.

The structure determination confirms the stereochemistry of the title compound, C(21)H(35)NO(3), obtained as an inter-mediate in the enanti-oselective synthesis of de-oxy-nojirimicine analogs. The system contains a pyrrolo-[1,2-a]azocine backbone, which was synthesized by a domino process involving a [2,3]-sigmatropic rearrangement. The incorporation of a chiral auxiliary (-)-menthyl, whose stereocentres are not involved during the synthesis, enables the assignation of absolute configuration. The crystal structure features O-H⋯O hydrogen bonds involving the hy-droxy groups as donors and the carbonyl groups as acceptors, which link the mol-ecules into chains running along [010].

Related literature

For the construction of the pyrrolo­[1,2-a]azocine backbone by the domino sequence, see: Clark et al. (2001 ▶); Muroni et al. (2006 ▶). For domino processes promoted by catalytic decomposition of diazo­compounds, see: Doyle et al. (1997 ▶). For [2,3]-sigmatropic rearrangement, see: Sweeney (2009 ▶); Zhang & Wang (2010 ▶). For manzamine alkaloids and other biologically active compounds containing the pyrrolo­[1,2-a]azocine subunit, see: Rao et al. (2006 ▶); Yap et al. (2011 ▶); Sun et al. (2011 ▶). For de­oxy­nojirimicine and imino­sugars, see: Asano et al. (2000 ▶); Watson et al. (2001 ▶). For chiral auxiliary (−)-menthyl, see: Wang et al. (2006 ▶).

Experimental

Crystal data

C21H35NO3

M = 349.5

Orthorhombic,

a = 10.7804 (8) Å

b = 7.7938 (7) Å

c = 23.8862 (17) Å

V = 2006.9 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 120 K

0.36 × 0.13 × 0.13 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2008 ▶) T min = 0.716, T max = 0.746

21709 measured reflections

3281 independent reflections

2331 reflections with I > 3σ(I)

R int = 0.048

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.047

S = 1.23

3281 reflections

230 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.23 e Å−3

Δρmin = −0.28 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SIR2011 (Burla et al., 2012 ▶); program(s) used to refine structure: JANA2006 (Petricek et al., 2006 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶) and ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812027900/bh2433sup1.cif

Supplementary material file. DOI: 10.1107/S1600536812027900/bh2433Isup2.cdx

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812027900/bh2433Isup3.hkl

Supplementary material file. DOI: 10.1107/S1600536812027900/bh2433Isup4.cml

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

C21H35NO3	Dx = 1.156 Mg m−3
Mr = 349.5	Melting point: 389 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2ac 2ab	Cell parameters from 192 reflections
a = 10.7804 (8) Å	θ = 3.8–17.2°
b = 7.7938 (7) Å	µ = 0.08 mm−1
c = 23.8862 (17) Å	T = 120 K
V = 2006.9 (3) Å3	Prism, colourless
Z = 4	0.36 × 0.13 × 0.13 mm
F(000) = 768

Bruker APEXII CCD diffractometer	3281 independent reflections
Radiation source: sealed X-ray tube	2331 reflections with I > 3σ(I)
Graphite monochromator	Rint = 0.048
ω scans	θmax = 30.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	h = −15→14
Tmin = 0.716, Tmax = 0.746	k = −10→4
21709 measured reflections	l = −33→33

Refinement on F	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.041	Weighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.0004F2)
wR(F2) = 0.047	(Δ/σ)max = 0.016
S = 1.23	Δρmax = 0.23 e Å−3
3281 reflections	Δρmin = −0.28 e Å−3
230 parameters	Extinction correction: B-C type 1 Gaussian isotropic
0 restraints	Extinction coefficient: 16900 (1800)
0 constraints

	x	y	z	Uiso*/Ueq
N1	0.67923 (4)	0.06933 (14)	0.867458 (19)	0.0178 (4)
C4	0.67762 (4)	−0.11800 (4)	0.865956 (9)	0.0220 (5)
C5	0.80174 (3)	−0.19770 (3)	0.849823 (11)	0.0257 (6)
C6	0.83930 (2)	−0.17312 (6)	0.788428 (13)	0.0300 (6)
C7	0.87823 (6)	0.0057 (2)	0.77279 (3)	0.0269 (6)
C8	0.80364 (17)	0.13680 (12)	0.76224 (5)	0.0248 (6)
C9	0.66451 (6)	0.12758 (8)	0.76547 (3)	0.0217 (5)
C10	0.61339 (12)	0.16447 (13)	0.82487 (7)	0.0164 (5)
C1	0.63656 (4)	0.35106 (14)	0.84420 (7)	0.0191 (5)
O1	0.54447 (13)	0.46881 (18)	0.82643 (6)	0.0257 (4)
C2	0.63894 (2)	0.34119 (7)	0.90814 (3)	0.0217 (5)
C3	0.67015 (2)	0.15400 (4)	0.92186 (3)	0.0210 (5)
C11	0.47217 (16)	0.1302 (2)	0.82373 (7)	0.0164 (5)
O2	0.41170 (12)	0.10136 (18)	0.78189 (5)	0.0266 (4)
O3	0.42289 (10)	0.13359 (17)	0.87513 (5)	0.0182 (4)
C12	0.28911 (11)	0.1047 (2)	0.88055 (3)	0.0181 (5)
C17	0.22301 (3)	0.27715 (11)	0.880303 (16)	0.0229 (6)
C16	0.08230 (4)	0.24991 (5)	0.88606 (2)	0.0268 (6)
C21	0.01309 (2)	0.42102 (2)	0.886679 (15)	0.0438 (8)
C15	0.05454 (3)	0.14406 (3)	0.93799 (2)	0.0280 (6)
C14	0.12697 (3)	−0.02306 (5)	0.940244 (13)	0.0253 (6)
C13	0.26755 (15)	0.00578 (9)	0.93465 (2)	0.0188 (5)
C18	0.34514 (5)	−0.16029 (4)	0.93837 (3)	0.0251 (6)
C20	0.32327 (3)	−0.25601 (4)	0.993247 (7)	0.0414 (8)
C19	0.32833 (4)	−0.27844 (2)	0.888694 (8)	0.0426 (8)
H4a	0.614688	−0.156111	0.840384	0.0264*
H4b	0.6521	−0.161351	0.901768	0.0264*
H5a	0.800812	−0.317901	0.858591	0.0309*
H5b	0.865733	−0.153207	0.873703	0.0309*
H6b	0.904465	−0.252127	0.779173	0.036*
H6a	0.772558	−0.209188	0.764565	0.036*
H7a	0.965749	0.027044	0.77019	0.0323*
H8a	0.840656	0.244258	0.75191	0.0298*
H9a	0.637241	0.016292	0.753417	0.0261*
H9b	0.629027	0.207304	0.739349	0.0261*
H1a	0.712104	0.393489	0.828043	0.023*
H2a	0.558255	0.368556	0.922615	0.0261*
H2b	0.703241	0.414569	0.92227	0.0261*
H3b	0.749001	0.148824	0.940459	0.0251*
H3a	0.603436	0.104084	0.94292	0.0251*
H12a	0.256529	0.038941	0.849922	0.0217*
H17b	0.24025	0.335803	0.845829	0.0275*
H17a	0.25235	0.34555	0.910993	0.0275*
H16a	0.053248	0.1875	0.853987	0.0322*
H21a	0.032739	0.48441	0.853379	0.0526*
H21c	−0.074614	0.400151	0.888079	0.0526*
H21b	0.037679	0.485998	0.91897	0.0526*
H15b	−0.032695	0.11983	0.939646	0.0336*
H15a	0.072245	0.210793	0.970814	0.0336*
H14a	0.099119	−0.097775	0.910867	0.0303*
H14b	0.10981	−0.080807	0.974889	0.0303*
H13a	0.296357	0.071257	0.96611	0.0225*
H18a	0.430002	−0.123046	0.937575	0.0302*
H20a	0.33419	−0.178579	1.024112	0.0496*
H20c	0.240371	−0.300948	0.993776	0.0496*
H20b	0.381516	−0.348697	0.996362	0.0496*
H19a	0.34236	−0.215556	0.854721	0.0512*
H19c	0.386534	−0.371357	0.89113	0.0512*
H19b	0.245414	−0.32338	0.88871	0.0512*
H1o	0.556 (2)	0.499 (3)	0.7944 (9)	0.0309*

	U11	U22	U33	U12	U13	U23
N1	0.0178 (7)	0.0180 (8)	0.0174 (7)	0.0028 (6)	−0.0002 (6)	0.0006 (6)
C4	0.0200 (9)	0.0191 (10)	0.0268 (10)	0.0010 (7)	−0.0007 (8)	0.0041 (8)
C5	0.0218 (10)	0.0180 (10)	0.0374 (11)	0.0050 (7)	−0.0012 (8)	−0.0013 (9)
C6	0.0215 (10)	0.0320 (12)	0.0364 (11)	0.0038 (9)	0.0023 (9)	−0.0108 (10)
C7	0.0169 (9)	0.0376 (12)	0.0263 (10)	−0.0026 (8)	0.0056 (8)	−0.0079 (10)
C8	0.0239 (9)	0.0303 (11)	0.0203 (9)	−0.0050 (9)	0.0069 (8)	−0.0030 (9)
C9	0.0211 (9)	0.0252 (10)	0.0189 (9)	0.0016 (8)	0.0046 (7)	−0.0009 (8)
C10	0.0148 (8)	0.0183 (9)	0.0162 (8)	0.0005 (7)	0.0025 (7)	0.0033 (8)
C1	0.0180 (8)	0.0179 (9)	0.0215 (9)	0.0000 (7)	0.0040 (7)	0.0033 (8)
O1	0.0307 (7)	0.0224 (7)	0.0241 (7)	0.0078 (6)	0.0055 (6)	0.0083 (6)
C2	0.0214 (9)	0.0205 (10)	0.0232 (9)	−0.0018 (8)	0.0017 (7)	−0.0020 (8)
C3	0.0173 (9)	0.0263 (10)	0.0193 (9)	0.0007 (8)	−0.0017 (7)	0.0004 (8)
C11	0.0193 (8)	0.0142 (9)	0.0159 (8)	0.0040 (7)	0.0016 (7)	0.0014 (8)
O2	0.0197 (6)	0.0408 (9)	0.0192 (7)	0.0014 (6)	−0.0014 (5)	−0.0028 (6)
O3	0.0139 (6)	0.0243 (7)	0.0164 (6)	−0.0016 (5)	0.0022 (5)	0.0009 (6)
C12	0.0132 (8)	0.0227 (10)	0.0184 (9)	−0.0017 (7)	0.0015 (6)	−0.0005 (8)
C17	0.0226 (9)	0.0239 (11)	0.0223 (10)	0.0032 (8)	0.0007 (8)	0.0037 (8)
C16	0.0189 (9)	0.0340 (12)	0.0276 (11)	0.0040 (9)	−0.0018 (8)	0.0000 (9)
C21	0.0283 (11)	0.0506 (16)	0.0527 (15)	0.0167 (11)	0.0056 (10)	0.0170 (13)
C15	0.0183 (9)	0.0321 (12)	0.0336 (11)	0.0022 (9)	0.0067 (8)	−0.0013 (10)
C14	0.0189 (9)	0.0251 (11)	0.0318 (11)	−0.0023 (8)	0.0052 (8)	0.0000 (9)
C13	0.0177 (8)	0.0202 (10)	0.0185 (9)	−0.0009 (7)	0.0014 (7)	−0.0001 (8)
C18	0.0202 (9)	0.0203 (10)	0.0348 (11)	0.0020 (8)	0.0071 (8)	0.0055 (9)
C20	0.0396 (13)	0.0359 (13)	0.0485 (13)	0.0092 (11)	0.0061 (11)	0.0186 (11)
C19	0.0566 (16)	0.0222 (12)	0.0492 (14)	0.0067 (11)	0.0135 (12)	−0.0031 (10)

N1—C4	1.4605 (11)	C11—O3	1.338 (2)
N1—C10	1.4450 (16)	O3—C12	1.4654 (16)
N1—C3	1.4607 (9)	C12—C17	1.5209 (17)
C4—C5	1.5247 (5)	C12—C13	1.5228 (11)
C4—H4a	0.9600	C12—H12a	0.9600
C4—H4b	0.9600	C17—C16	1.5379 (6)
C5—C6	1.5335 (4)	C17—H17b	0.9600
C5—H5a	0.9600	C17—H17a	0.9600
C5—H5b	0.9600	C16—C21	1.5282 (4)
C6—C7	1.5029 (18)	C16—C15	1.5195 (7)
C6—H6b	0.9600	C16—H16a	0.9600
C6—H6a	0.9600	C21—H21a	0.9600
C7—C8	1.324 (2)	C21—H21c	0.9600
C7—H7a	0.9600	C21—H21b	0.9600
C8—C9	1.5035 (19)	C15—C14	1.5196 (5)
C8—H8a	0.9600	C15—H15b	0.9600
C9—C10	1.5492 (17)	C15—H15a	0.9600
C9—H9a	0.9600	C14—C13	1.5379 (16)
C9—H9b	0.9600	C14—H14a	0.9600
C10—C1	1.5461 (16)	C14—H14b	0.9600
C10—C11	1.546 (2)	C13—C18	1.5436 (11)
C1—O1	1.4169 (17)	C13—H13a	0.9600
C1—C2	1.5294 (18)	C18—C20	1.5266 (6)
C1—H1a	0.9600	C18—C19	1.5128 (6)
O1—H1o	0.81 (2)	C18—H18a	0.9600
C2—C3	1.5327 (6)	C20—H20a	0.9600
C2—H2a	0.9600	C20—H20c	0.9600
C2—H2b	0.9600	C20—H20b	0.9600
C3—H3b	0.9600	C19—H19a	0.9600
C3—H3a	0.9600	C19—H19c	0.9600
C11—O2	1.214 (2)	C19—H19b	0.9600
C4—N1—C10	119.33 (6)	C11—O3—C12	117.97 (11)
C4—N1—C3	118.20 (5)	O3—C12—C17	108.98 (11)
C10—N1—C3	111.19 (8)	O3—C12—C13	107.64 (10)
N1—C4—C5	113.76 (3)	O3—C12—H12a	112.00
N1—C4—H4a	109.47	C17—C12—C13	112.28 (7)
N1—C4—H4b	109.47	C17—C12—H12a	107.00
C5—C4—H4a	109.47	C13—C12—H12a	109.00
C5—C4—H4b	109.47	C12—C17—C16	109.87 (7)
H4a—C4—H4b	105.00	C12—C17—H17b	109.47
C4—C5—C6	115.00 (2)	C12—C17—H17a	109.47
C4—C5—H5a	109.47	C16—C17—H17b	109.47
C4—C5—H5b	109.47	C16—C17—H17a	109.47
C6—C5—H5a	109.47	H17b—C17—H17a	109.00
C6—C5—H5b	109.47	C17—C16—C21	111.22 (4)
H5a—C5—H5b	103.00	C17—C16—C15	110.02 (4)
C5—C6—C7	115.30 (4)	C17—C16—H16a	109.00
C5—C6—H6b	109.47	C21—C16—C15	111.69 (4)
C5—C6—H6a	109.47	C21—C16—H16a	107.00
C7—C6—H6b	109.47	C15—C16—H16a	108.00
C7—C6—H6a	109.47	C16—C21—H21a	109.47
H6b—C6—H6a	103.00	C16—C21—H21c	109.47
C6—C7—C8	126.38 (9)	C16—C21—H21b	109.47
C6—C7—H7a	117.00	H21a—C21—H21c	109.00
C8—C7—H7a	117.00	H21a—C21—H21b	109.00
C7—C8—C9	124.00 (10)	H21c—C21—H21b	109.47
C7—C8—H8a	118.00	C16—C15—C14	113.14 (3)
C9—C8—H8a	118.00	C16—C15—H15b	109.00
C8—C9—C10	113.14 (8)	C16—C15—H15a	109.47
C8—C9—H9a	109.47	C14—C15—H15b	109.47
C8—C9—H9b	109.47	C14—C15—H15a	109.47
C10—C9—H9a	109.47	H15b—C15—H15a	106.00
C10—C9—H9b	109.47	C15—C14—C13	112.21 (4)
H9a—C9—H9b	105.53	C15—C14—H14a	109.47
N1—C10—C9	112.01 (8)	C15—C14—H14b	109.47
N1—C10—C1	101.14 (11)	C13—C14—H14a	109.47
N1—C10—C11	114.03 (11)	C13—C14—H14b	109.47
C9—C10—C1	112.99 (10)	H14a—C14—H14b	107.00
C9—C10—C11	107.60 (11)	C12—C13—C14	107.36 (9)
C1—C10—C11	109.07 (10)	C12—C13—C18	113.00 (9)
C10—C1—O1	114.00 (10)	C12—C13—H13a	110.00
C10—C1—C2	104.69 (10)	C14—C13—C18	113.97 (6)
C10—C1—H1a	110.00	C14—C13—H13a	109.00
O1—C1—C2	110.07 (10)	C18—C13—H13a	103.00
O1—C1—H1a	105.00	C13—C18—C20	112.05 (5)
C2—C1—H1a	114.00	C13—C18—C19	113.60 (5)
C1—O1—H1o	111.1 (16)	C13—C18—H18a	105.00
C1—C2—C3	105.37 (6)	C20—C18—C19	110.95 (2)
C1—C2—H2a	109.47	C20—C18—H18a	108.00
C1—C2—H2b	109.47	C19—C18—H18a	106.00
C3—C2—H2a	109.47	C18—C20—H20a	109.47
C3—C2—H2b	109.47	C18—C20—H20c	109.47
H2a—C2—H2b	113.00	C18—C20—H20b	109.47
N1—C3—C2	104.74 (6)	H20a—C20—H20c	109.47
N1—C3—H3b	109.47	H20a—C20—H20b	109.47
N1—C3—H3a	109.47	H20c—C20—H20b	109.47
C2—C3—H3b	109.47	C18—C19—H19a	109.47
C2—C3—H3a	109.47	C18—C19—H19c	109.47
H3b—C3—H3a	114.00	C18—C19—H19b	109.47
C10—C11—O2	125.10 (15)	H19a—C19—H19c	109.47
C10—C11—O3	111.82 (14)	H19a—C19—H19b	109.47
O2—C11—O3	123.07 (16)	H19c—C19—H19b	109.00

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···O2i	0.81 (2)	2.02 (2)	2.8259 (19)	174 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1o⋯O2i	0.81 (2)	2.02 (2)	2.8259 (19)	174 (2)

Symmetry code: (i) .