organic compounds
Methyl 2-benzyl-1-benzyloxy-6a-methyl-1,2,3,3a,4,6a-hexahydrocyclopenta[b]pyrrole-3a-carboxylate: hydrogen-bonded R44(24) sheets
aDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland., bDepartamento de Química Inorgánica y Orgánica, Universidad de Jaén, 23071 Jaén, Spain, and cDepartamento de Química, Universidad del Valle, AA 25360 Cali, Colombia
*Correspondence e-mail: che562@abdn.ac.uk
In the title 24H27NO3, molecules are linked by two C–H⋯O hydrogen bonds into R44(24) sheets.
CComment
Pyrrolidine-containing derivatives are present in a large number of biologically active natural products and numerous therapeutic agents. Radical cyclizations have emerged as a useful synthetic tool and have been reported in the synthesis of via the generation and trapping of nitrogen-centred radicals e.g. aminyl, iminyl, amidyl radicals etc. (Esker & Newcomb, 1993; Fallis & Brinza, 1997; Bowman et al. 1996; Guindon et al., 2001) However, no reports about the capture of neutral alkyl–oxyaminyl radicals by a multiple function have been published up to date for the preparation of fused pyrrolidine derivatives. We describe here a fused pyrrolidine derivative, (I), prepared for the first time via an alkyl–oxyaminyl radical, which has been generated through the reductive intermolecular or intramolecular addition of carbon radicals to the carbon atom of oxime (Friestad, 2001; Naito et al., 2000; Tauh & Fallis, 1999; Marco-Contelles et al., 1996; Enholm et al., 1990). We carried out this reaction from methyl 2-[(E)-1-(benzyloxyimino)ethyl]-5-bromo-2-cinnamylpent-4-enoate by a double bond in a cascade process yielding the title compound, (I). This reaction involves two sequential 5-exo ring closures involving vinyl and neutral alkyl–oxyaminyl radicals, in a chain radical reaction, in which the attack of the radical is stereo-controlled by the carboxymethyl group, and hence determining the stereochemistry of the new bonds on the opposite face to that group.
and related pyrrolidinic compoundsThe title molecule, (I), is shown in Fig. 1. There are no unusual bonds lengths or angles in the structure. The puckering of the two five-membered rings N1/C2/C3/C3A/C6A and C3A/C4/C5/C6/C6A as defined by the pseudorotation parameters P and τ(M) (Rao et al., 1981), are, for the former, P = 182.4 (1)°, τ(M) = 48.6 (1)°, reference bond N1—C2, corresponding to a twist on N1—C2 and, for the latter, P = 340.4 (6)°, τ(M) = 12.2 (1)°, reference bond C3A—C4, corresponding to an envelope on C3A.
Two C—H⋯O hydrogen bonds are involved in the supramolecular stucture (Table 1). C5—H5⋯O1( + x, − y, 1 − z) forms a C(6) chain (Fig. 2) (Bernstein et al., 1995) and C27—H27B⋯O32A forms a C(7) chain (Fig. 3), both of which run parallel to the a axis. The latter hydrogen bond links antiparallel C6 chains of the former type into a sheet consisting of a network of R44(24) rings which lies parallel to (010) (Fig. 4). Atom C5 is a hydrogen donor to O1 in the molecule at ( + x, − y, 1 − z), atom C2a in this molecule is a hydrogen donor to O1 in the molecule at (x, − y, − − z), C27 in this molecule is a hydrogen donor to O32A in the molecule at (− + x, − y, 1 − z), while C5 is a hydrogen donor to O32A in the molecule at (x, y, z). Two such sheets occur in the one in the range 0.0 > y > 0.5 and 0.5 > y > 1.0. There are no interactions between adjacent sheets, C—H⋯π or π–π interactions being absent.
Experimental
A solution of methyl 2-[(E)-1-(benzyloxyimino)ethyl]-5-bromo-2-cinnamylpent-4-enoate (350 mg, 0.77 mmol), 2,2′-azobisisobutyronitrile (39 mg, 0.23 mmol) and tributyltin hydride (0.26 ml, 0.92 mmol) in cyclohexane (39 ml) was degassed for 1 h by bubbling dry argon, and subsequently stirred at 353 K for 6–8 h. After cooling to room temperature the solution was evaporated under low pressure to dryness. Purification of the crude mixture by flash with 5% (v/v) AcOEt/hexanes yielded a white solid (63 mg, 22% yield) mp 355 K. HRMS (EI) calcd for C24H27NO3 377.19909, found 377.19907. The solid was recrystallized from ethanol producing white crystals suitable for X-ray analysis.
Crystal data
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Data collection
Refinement
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H atoms were treated as riding atoms, with aromatic C—H = 0.95 Å, CH2 C—H = 0.99 Å, both with Uiso(H) = 1.2Ueq(C), and methyl C—H = 0.98 Å, with Uiso(H) = 1.5Ueq(C).
Data collection: COLLECT (Hooft, 2004); cell DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL (McArdle, 2003 and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999).
Supporting information
10.1107/S1600536805040742/lh6566sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536805040742/lh6566Isup2.hkl
A solution of methyl 2-[(E)-1-(benzyloxyimino)ethyl]-5-bromo-2-cinnamylpent-4-enoate (350 mg, 0.77 mmol), 2,2'-azobisisobutironitrile (39 mg, 0.23 mmol) and tributyltin hydride (0.26 ml, 0.92 mmol) in cyclohexane (39 ml) was degassed for 1 h by bubbling dry argon, and subsequently stirred at 353 K for 6–8 h. After cooling to room temperature the solution was evaporated under low pressure to dryness. Purification of the crude mixture by flash
with 5% (v/v) AcOEt/hexanes yielded a white solid (63 mg, 22% yield) mp 355 K. HRMS (EI) calcd for C24H27NO3 377.19909, found 377.19907. The solid was recrystallized from hexanes producing white crystals suitable for X-ray analysis.H atoms were treated as riding atoms, with aromatic C—H = 0.95 Å, CH2 C—H = 0.99 Å, both with Uiso(H) = 1.2Ueq(C), and methyl C—H = 0.98 Å, with Uiso(H) = 1.5Ueq(C).
Data collection: COLLECT (Hooft, 2004); cell
DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL (McArdle, 2003 and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999).C24H27NO3 | Dx = 1.233 Mg m−3 |
Mr = 377.47 | Melting point: 355 K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 4921 reflections |
a = 8.8410 (17) Å | θ = 6.4–28.5° |
b = 20.584 (4) Å | µ = 0.08 mm−1 |
c = 22.344 (2) Å | T = 120 K |
V = 4066.2 (12) Å3 | Plate, colourless |
Z = 8 | 0.38 × 0.33 × 0.12 mm |
F(000) = 1616 |
Bruker–Nonius KappaCCD diffractometer | 4921 independent reflections |
Radiation source: fine-focus sealed tube | 3477 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
ϕ–ω scans | θmax = 28.5°, θmin = 6.4° |
Absorption correction: multi-scan [SADABS (Sheldrick, 2003) and EVALCCD (Duisenberg et al., 2003)] | h = −11→11 |
Tmin = 0.970, Tmax = 0.990 | k = −26→26 |
48795 measured reflections | l = −29→27 |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0174P)2 + 3.2146P] where P = (Fo2 + 2Fc2)/3 |
4921 reflections | (Δ/σ)max = 0.001 |
255 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C24H27NO3 | V = 4066.2 (12) Å3 |
Mr = 377.47 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 8.8410 (17) Å | µ = 0.08 mm−1 |
b = 20.584 (4) Å | T = 120 K |
c = 22.344 (2) Å | 0.38 × 0.33 × 0.12 mm |
Bruker–Nonius KappaCCD diffractometer | 4921 independent reflections |
Absorption correction: multi-scan [SADABS (Sheldrick, 2003) and EVALCCD (Duisenberg et al., 2003)] | 3477 reflections with I > 2σ(I) |
Tmin = 0.970, Tmax = 0.990 | Rint = 0.041 |
48795 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.36 e Å−3 |
4921 reflections | Δρmin = −0.23 e Å−3 |
255 parameters |
Experimental. The Tmin and Tmax values reported are those calculated from the SHELX SIZE command. The ratio of experimental transmission factors from SADABS is 0.239891 |
x | y | z | Uiso*/Ueq | ||
N1 | 0.34560 (14) | 0.15468 (6) | 0.61087 (5) | 0.0175 (3) | |
O1 | 0.25222 (12) | 0.14741 (5) | 0.55813 (5) | 0.0203 (2) | |
C17 | 0.15344 (18) | 0.09243 (8) | 0.56498 (7) | 0.0227 (3) | |
C11 | 0.07975 (17) | 0.08382 (7) | 0.50510 (7) | 0.0207 (3) | |
C12 | 0.15277 (19) | 0.05002 (8) | 0.46007 (8) | 0.0276 (4) | |
C13 | 0.0873 (2) | 0.04383 (10) | 0.40405 (8) | 0.0399 (5) | |
C14 | −0.0513 (3) | 0.07179 (10) | 0.39271 (9) | 0.0470 (6) | |
C15 | −0.1252 (2) | 0.10536 (10) | 0.43739 (11) | 0.0447 (5) | |
C16 | −0.06004 (19) | 0.11148 (8) | 0.49326 (9) | 0.0322 (4) | |
C2 | 0.32646 (16) | 0.22132 (7) | 0.63345 (7) | 0.0178 (3) | |
C27 | 0.17335 (17) | 0.22926 (7) | 0.66419 (7) | 0.0219 (3) | |
C21 | 0.13840 (17) | 0.29887 (7) | 0.68005 (7) | 0.0192 (3) | |
C22 | 0.04210 (18) | 0.33563 (8) | 0.64441 (7) | 0.0228 (3) | |
C23 | 0.01202 (19) | 0.40019 (9) | 0.65715 (8) | 0.0303 (4) | |
C24 | 0.0776 (2) | 0.42919 (9) | 0.70642 (9) | 0.0351 (4) | |
C25 | 0.1720 (2) | 0.39336 (9) | 0.74298 (9) | 0.0332 (4) | |
C26 | 0.20282 (18) | 0.32876 (8) | 0.72997 (7) | 0.0255 (4) | |
C3 | 0.46432 (17) | 0.22611 (8) | 0.67422 (7) | 0.0223 (3) | |
C3A | 0.59306 (17) | 0.19107 (8) | 0.63972 (7) | 0.0210 (3) | |
C31A | 0.68804 (18) | 0.14638 (8) | 0.67829 (8) | 0.0257 (4) | |
O31A | 0.82136 (14) | 0.13675 (7) | 0.67205 (7) | 0.0465 (4) | |
O32A | 0.60534 (14) | 0.11550 (6) | 0.71958 (5) | 0.0293 (3) | |
C32A | 0.6850 (3) | 0.06932 (9) | 0.75659 (9) | 0.0434 (5) | |
C4 | 0.6937 (2) | 0.23914 (9) | 0.60414 (9) | 0.0342 (4) | |
C5 | 0.6389 (2) | 0.23438 (9) | 0.54132 (9) | 0.0334 (4) | |
C6 | 0.53930 (19) | 0.18767 (9) | 0.53393 (8) | 0.0285 (4) | |
C6A | 0.50606 (17) | 0.15025 (8) | 0.59043 (7) | 0.0192 (3) | |
C61A | 0.54885 (19) | 0.07899 (8) | 0.58369 (8) | 0.0277 (4) | |
H17A | 0.0767 | 0.1009 | 0.5963 | 0.027* | |
H17B | 0.2117 | 0.0532 | 0.5761 | 0.027* | |
H12 | 0.2487 | 0.0309 | 0.4676 | 0.033* | |
H13 | 0.1379 | 0.0203 | 0.3735 | 0.048* | |
H14 | −0.0958 | 0.0680 | 0.3542 | 0.056* | |
H15 | −0.2213 | 0.1243 | 0.4297 | 0.054* | |
H16 | −0.1114 | 0.1348 | 0.5238 | 0.039* | |
H2 | 0.3358 | 0.2531 | 0.5998 | 0.021* | |
H27A | 0.0931 | 0.2125 | 0.6374 | 0.026* | |
H27B | 0.1722 | 0.2027 | 0.7011 | 0.026* | |
H22 | −0.0041 | 0.3160 | 0.6105 | 0.027* | |
H23 | −0.0536 | 0.4245 | 0.6320 | 0.036* | |
H24 | 0.0579 | 0.4736 | 0.7151 | 0.042* | |
H25 | 0.2162 | 0.4130 | 0.7772 | 0.040* | |
H26 | 0.2684 | 0.3047 | 0.7553 | 0.031* | |
H3A | 0.4447 | 0.2045 | 0.7130 | 0.027* | |
H3B | 0.4910 | 0.2721 | 0.6818 | 0.027* | |
H32A | 0.7229 | 0.0337 | 0.7316 | 0.065* | |
H32B | 0.6160 | 0.0519 | 0.7869 | 0.065* | |
H32C | 0.7702 | 0.0910 | 0.7763 | 0.065* | |
H4A | 0.6817 | 0.2839 | 0.6196 | 0.041* | |
H4B | 0.8016 | 0.2266 | 0.6069 | 0.041* | |
H5 | 0.6724 | 0.2621 | 0.5100 | 0.040* | |
H6 | 0.4927 | 0.1784 | 0.4966 | 0.034* | |
H61A | 0.5236 | 0.0556 | 0.6206 | 0.041* | |
H61B | 0.6577 | 0.0754 | 0.5760 | 0.041* | |
H61C | 0.4928 | 0.0600 | 0.5501 | 0.041* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0178 (6) | 0.0182 (7) | 0.0165 (6) | 0.0012 (5) | −0.0025 (5) | −0.0002 (5) |
O1 | 0.0219 (5) | 0.0197 (6) | 0.0193 (5) | −0.0041 (4) | −0.0061 (5) | 0.0007 (4) |
C17 | 0.0247 (8) | 0.0193 (8) | 0.0241 (8) | −0.0045 (6) | −0.0004 (7) | −0.0007 (6) |
C11 | 0.0206 (8) | 0.0161 (8) | 0.0254 (8) | −0.0040 (6) | −0.0029 (6) | 0.0010 (6) |
C12 | 0.0251 (8) | 0.0281 (9) | 0.0295 (9) | −0.0037 (7) | −0.0002 (7) | −0.0024 (7) |
C13 | 0.0526 (12) | 0.0421 (11) | 0.0251 (9) | −0.0177 (10) | 0.0004 (9) | −0.0054 (8) |
C14 | 0.0621 (14) | 0.0423 (12) | 0.0366 (11) | −0.0256 (11) | −0.0275 (11) | 0.0143 (10) |
C15 | 0.0361 (11) | 0.0311 (11) | 0.0670 (15) | −0.0054 (9) | −0.0284 (11) | 0.0132 (10) |
C16 | 0.0256 (9) | 0.0221 (9) | 0.0488 (11) | 0.0010 (7) | −0.0056 (8) | −0.0010 (8) |
C2 | 0.0183 (7) | 0.0142 (7) | 0.0209 (8) | −0.0009 (6) | 0.0004 (6) | 0.0012 (6) |
C27 | 0.0193 (8) | 0.0186 (8) | 0.0277 (8) | −0.0018 (6) | 0.0040 (6) | 0.0014 (7) |
C21 | 0.0145 (7) | 0.0204 (8) | 0.0229 (8) | −0.0018 (6) | 0.0074 (6) | 0.0011 (6) |
C22 | 0.0185 (7) | 0.0260 (9) | 0.0238 (8) | −0.0021 (6) | 0.0031 (6) | 0.0004 (7) |
C23 | 0.0215 (8) | 0.0254 (9) | 0.0440 (11) | 0.0044 (7) | 0.0025 (8) | 0.0060 (8) |
C24 | 0.0245 (9) | 0.0237 (9) | 0.0573 (12) | 0.0026 (7) | 0.0066 (9) | −0.0105 (9) |
C25 | 0.0263 (9) | 0.0353 (10) | 0.0380 (10) | −0.0031 (8) | 0.0017 (8) | −0.0159 (8) |
C26 | 0.0201 (8) | 0.0305 (9) | 0.0259 (8) | 0.0019 (7) | 0.0006 (7) | −0.0015 (7) |
C3 | 0.0208 (8) | 0.0216 (9) | 0.0245 (8) | 0.0030 (6) | −0.0029 (7) | −0.0054 (7) |
C3A | 0.0191 (7) | 0.0179 (8) | 0.0260 (8) | −0.0017 (6) | −0.0004 (6) | −0.0004 (6) |
C31A | 0.0213 (8) | 0.0267 (9) | 0.0290 (9) | 0.0026 (7) | −0.0072 (7) | −0.0069 (7) |
O31A | 0.0217 (7) | 0.0610 (10) | 0.0567 (9) | 0.0125 (6) | −0.0081 (6) | −0.0013 (7) |
O32A | 0.0356 (7) | 0.0253 (6) | 0.0270 (6) | 0.0038 (5) | −0.0079 (5) | 0.0021 (5) |
C32A | 0.0662 (14) | 0.0262 (10) | 0.0380 (11) | 0.0072 (10) | −0.0269 (10) | −0.0011 (8) |
C4 | 0.0307 (9) | 0.0247 (9) | 0.0473 (11) | −0.0084 (7) | 0.0099 (8) | −0.0009 (8) |
C5 | 0.0294 (9) | 0.0318 (10) | 0.0389 (10) | 0.0067 (8) | 0.0146 (8) | 0.0131 (8) |
C6 | 0.0255 (9) | 0.0388 (10) | 0.0212 (8) | 0.0075 (8) | 0.0051 (7) | 0.0056 (7) |
C6A | 0.0185 (7) | 0.0204 (8) | 0.0187 (7) | 0.0015 (6) | 0.0006 (6) | −0.0005 (6) |
C61A | 0.0260 (8) | 0.0248 (9) | 0.0322 (9) | 0.0051 (7) | −0.0036 (7) | −0.0079 (7) |
N1—O1 | 1.4466 (15) | C23—H23 | 0.95 |
N1—C2 | 1.4713 (19) | C24—C25 | 1.382 (3) |
N1—C6A | 1.4931 (19) | C24—H24 | 0.95 |
O1—C17 | 1.4377 (18) | C25—C26 | 1.388 (2) |
C17—C11 | 1.499 (2) | C25—H25 | 0.95 |
C17—H17A | 0.99 | C26—H26 | 0.95 |
C17—H17B | 0.99 | C3—C3A | 1.552 (2) |
C11—C12 | 1.383 (2) | C3—H3A | 0.99 |
C11—C16 | 1.386 (2) | C3—H3B | 0.99 |
C12—C13 | 1.385 (3) | C3A—C31A | 1.515 (2) |
C12—H12 | 0.95 | C3A—C4 | 1.550 (2) |
C13—C14 | 1.377 (3) | C3A—C6A | 1.584 (2) |
C13—H13 | 0.95 | C31A—O31A | 1.203 (2) |
C14—C15 | 1.379 (3) | C31A—O32A | 1.338 (2) |
C14—H14 | 0.95 | O32A—C32A | 1.444 (2) |
C15—C16 | 1.381 (3) | C32A—H32A | 0.98 |
C15—H15 | 0.95 | C32A—H32B | 0.98 |
C16—H16 | 0.95 | C32A—H32C | 0.98 |
C2—C3 | 1.525 (2) | C4—C5 | 1.488 (3) |
C2—C27 | 1.527 (2) | C4—H4A | 0.99 |
C2—H2 | 1.00 | C4—H4B | 0.99 |
C27—C21 | 1.508 (2) | C5—C6 | 1.314 (3) |
C27—H27A | 0.99 | C5—H5 | 0.95 |
C27—H27B | 0.99 | C6—C6A | 1.508 (2) |
C21—C22 | 1.390 (2) | C6—H6 | 0.95 |
C21—C26 | 1.395 (2) | C6A—C61A | 1.522 (2) |
C22—C23 | 1.385 (2) | C61A—H61A | 0.98 |
C22—H22 | 0.95 | C61A—H61B | 0.98 |
C23—C24 | 1.380 (3) | C61A—H61C | 0.98 |
O1—N1—C2 | 108.07 (11) | C24—C25—C26 | 120.40 (17) |
O1—N1—C6A | 106.66 (11) | C24—C25—H25 | 119.8 |
C2—N1—C6A | 105.73 (12) | C26—C25—H25 | 119.8 |
C17—O1—N1 | 109.96 (11) | C25—C26—C21 | 120.64 (16) |
O1—C17—C11 | 105.19 (12) | C25—C26—H26 | 119.7 |
O1—C17—H17A | 110.7 | C21—C26—H26 | 119.7 |
C11—C17—H17A | 110.7 | C2—C3—C3A | 105.04 (12) |
O1—C17—H17B | 110.7 | C2—C3—H3A | 110.7 |
C11—C17—H17B | 110.7 | C3A—C3—H3A | 110.7 |
H17A—C17—H17B | 108.8 | C2—C3—H3B | 110.7 |
C12—C11—C16 | 118.94 (16) | C3A—C3—H3B | 110.7 |
C12—C11—C17 | 120.39 (15) | H3A—C3—H3B | 108.8 |
C16—C11—C17 | 120.63 (15) | C31A—C3A—C4 | 111.19 (14) |
C11—C12—C13 | 120.56 (17) | C31A—C3A—C3 | 113.96 (13) |
C11—C12—H12 | 119.7 | C4—C3A—C3 | 112.26 (13) |
C13—C12—H12 | 119.7 | C31A—C3A—C6A | 110.03 (13) |
C14—C13—C12 | 119.99 (19) | C4—C3A—C6A | 105.10 (13) |
C14—C13—H13 | 120.0 | C3—C3A—C6A | 103.63 (12) |
C12—C13—H13 | 120.0 | O31A—C31A—O32A | 122.47 (17) |
C13—C14—C15 | 119.87 (18) | O31A—C31A—C3A | 125.26 (17) |
C13—C14—H14 | 120.1 | O32A—C31A—C3A | 112.21 (13) |
C15—C14—H14 | 120.1 | C31A—O32A—C32A | 116.18 (15) |
C14—C15—C16 | 120.15 (19) | O32A—C32A—H32A | 109.5 |
C14—C15—H15 | 119.9 | O32A—C32A—H32B | 109.5 |
C16—C15—H15 | 119.9 | H32A—C32A—H32B | 109.5 |
C15—C16—C11 | 120.48 (18) | O32A—C32A—H32C | 109.5 |
C15—C16—H16 | 119.8 | H32A—C32A—H32C | 109.5 |
C11—C16—H16 | 119.8 | H32B—C32A—H32C | 109.5 |
N1—C2—C3 | 99.98 (12) | C5—C4—C3A | 104.79 (14) |
N1—C2—C27 | 110.86 (12) | C5—C4—H4A | 110.8 |
C3—C2—C27 | 115.67 (13) | C3A—C4—H4A | 110.8 |
N1—C2—H2 | 110.0 | C5—C4—H4B | 110.8 |
C3—C2—H2 | 110.0 | C3A—C4—H4B | 110.8 |
C27—C2—H2 | 110.0 | H4A—C4—H4B | 108.9 |
C21—C27—C2 | 112.90 (12) | C6—C5—C4 | 112.63 (16) |
C21—C27—H27A | 109.0 | C6—C5—H5 | 123.7 |
C2—C27—H27A | 109.0 | C4—C5—H5 | 123.7 |
C21—C27—H27B | 109.0 | C5—C6—C6A | 113.52 (16) |
C2—C27—H27B | 109.0 | C5—C6—H6 | 123.2 |
H27A—C27—H27B | 107.8 | C6A—C6—H6 | 123.2 |
C22—C21—C26 | 117.91 (15) | N1—C6A—C6 | 114.21 (13) |
C22—C21—C27 | 120.55 (14) | N1—C6A—C61A | 108.98 (13) |
C26—C21—C27 | 121.54 (14) | C6—C6A—C61A | 111.16 (13) |
C23—C22—C21 | 121.49 (16) | N1—C6A—C3A | 102.49 (12) |
C23—C22—H22 | 119.3 | C6—C6A—C3A | 102.50 (13) |
C21—C22—H22 | 119.3 | C61A—C6A—C3A | 117.33 (13) |
C24—C23—C22 | 119.89 (17) | C6A—C61A—H61A | 109.5 |
C24—C23—H23 | 120.1 | C6A—C61A—H61B | 109.5 |
C22—C23—H23 | 120.1 | H61A—C61A—H61B | 109.5 |
C23—C24—C25 | 119.65 (17) | C6A—C61A—H61C | 109.5 |
C23—C24—H24 | 120.2 | H61A—C61A—H61C | 109.5 |
C25—C24—H24 | 120.2 | H61B—C61A—H61C | 109.5 |
C2—N1—O1—C17 | −125.72 (12) | C2—C3—C3A—C6A | −16.77 (16) |
C6A—N1—O1—C17 | 121.00 (13) | C4—C3A—C31A—O31A | −17.8 (2) |
N1—O1—C17—C11 | −171.95 (11) | C3—C3A—C31A—O31A | −145.89 (17) |
O1—C17—C11—C12 | 83.28 (18) | C6A—C3A—C31A—O31A | 98.2 (2) |
O1—C17—C11—C16 | −94.45 (17) | C4—C3A—C31A—O32A | 165.07 (13) |
C16—C11—C12—C13 | −0.1 (2) | C3—C3A—C31A—O32A | 36.98 (18) |
C17—C11—C12—C13 | −177.82 (16) | C6A—C3A—C31A—O32A | −78.90 (16) |
C11—C12—C13—C14 | 0.4 (3) | O31A—C31A—O32A—C32A | −0.2 (2) |
C12—C13—C14—C15 | −0.7 (3) | C3A—C31A—O32A—C32A | 177.03 (13) |
C13—C14—C15—C16 | 0.6 (3) | C31A—C3A—C4—C5 | 130.43 (15) |
C14—C15—C16—C11 | −0.3 (3) | C3—C3A—C4—C5 | −100.56 (16) |
C12—C11—C16—C15 | 0.0 (2) | C6A—C3A—C4—C5 | 11.41 (17) |
C17—C11—C16—C15 | 177.75 (16) | C3A—C4—C5—C6 | −7.3 (2) |
O1—N1—C2—C3 | −163.08 (11) | C4—C5—C6—C6A | −0.5 (2) |
C6A—N1—C2—C3 | −49.17 (14) | O1—N1—C6A—C6 | 43.33 (16) |
O1—N1—C2—C27 | 74.40 (14) | C2—N1—C6A—C6 | −71.55 (16) |
C6A—N1—C2—C27 | −171.70 (12) | O1—N1—C6A—C61A | −81.64 (14) |
N1—C2—C27—C21 | −171.53 (13) | C2—N1—C6A—C61A | 163.48 (12) |
C3—C2—C27—C21 | 75.59 (17) | O1—N1—C6A—C3A | 153.37 (11) |
C2—C27—C21—C22 | 100.61 (17) | C2—N1—C6A—C3A | 38.49 (14) |
C2—C27—C21—C26 | −78.34 (18) | C5—C6—C6A—N1 | 117.80 (16) |
C26—C21—C22—C23 | 0.9 (2) | C5—C6—C6A—C61A | −118.39 (16) |
C27—C21—C22—C23 | −178.05 (15) | C5—C6—C6A—C3A | 7.77 (18) |
C21—C22—C23—C24 | −0.4 (3) | C31A—C3A—C6A—N1 | 110.13 (14) |
C22—C23—C24—C25 | −0.5 (3) | C4—C3A—C6A—N1 | −130.07 (13) |
C23—C24—C25—C26 | 0.9 (3) | C3—C3A—C6A—N1 | −12.09 (15) |
C24—C25—C26—C21 | −0.4 (3) | C31A—C3A—C6A—C6 | −131.22 (13) |
C22—C21—C26—C25 | −0.5 (2) | C4—C3A—C6A—C6 | −11.43 (15) |
C27—C21—C26—C25 | 178.44 (15) | C3—C3A—C6A—C6 | 106.55 (14) |
N1—C2—C3—C3A | 39.62 (15) | C31A—C3A—C6A—C61A | −9.17 (19) |
C27—C2—C3—C3A | 158.67 (13) | C4—C3A—C6A—C61A | 110.63 (16) |
C2—C3—C3A—C31A | −136.34 (13) | C3—C3A—C6A—C61A | −131.39 (14) |
C2—C3—C3A—C4 | 96.12 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O1i | 0.95 | 2.51 | 3.444 (2) | 169 |
C27—H27B···O32Aii | 0.99 | 2.59 | 3.548 (2) | 163 |
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) x−1/2, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C24H27NO3 |
Mr | 377.47 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 120 |
a, b, c (Å) | 8.8410 (17), 20.584 (4), 22.344 (2) |
V (Å3) | 4066.2 (12) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.38 × 0.33 × 0.12 |
Data collection | |
Diffractometer | Bruker–Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan [SADABS (Sheldrick, 2003) and EVALCCD (Duisenberg et al., 2003)] |
Tmin, Tmax | 0.970, 0.990 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 48795, 4921, 3477 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.671 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.109, 1.11 |
No. of reflections | 4921 |
No. of parameters | 255 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.23 |
Computer programs: COLLECT (Hooft, 2004), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SHELXS97 (Sheldrick, 1997), OSCAIL (McArdle, 2003 and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O1i | 0.95 | 2.51 | 3.444 (2) | 169 |
C27—H27B···O32Aii | 0.99 | 2.59 | 3.548 (2) | 163 |
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) x−1/2, y, −z+3/2. |
Acknowledgements
X-ray data were collected at the Servicios Técnicos de Investigación, Universidad de Jaén. JC and MN thank the Consejería de Educación y Ciencia (Junta de Andalucía, Spain) and the Universidad de Jaén for financial support. LMJ and AEL thank COLCIENCIAS and Universidad del Valle for financial support of this work.
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Pyrrolidine-containing derivatives are present in a large number of biologically active natural products and numerous therapeutic agents. Radical cyclizations have emerged as a useful synthetic tool and have been reported in the synthesis of alkaloids and related pyrrolidinic compounds via generation and trapping of nitrogen-centered radicals e.g. aminyl, iminyl, amidyl radicals etc. (Esker & Newcomb, 1993; Fallis & Brinza, 1997; Bowman et al. 1996; Guindon et al., 2001) However, no reports about the capture of neutral alkyl–oxyaminyl radicals by a multiple function have been published up to date for the preparation of fused pyrrolidine derivatives. We describe here a fused pyrrolidine derivative, (I), prepared for the first time via an alkyl–oxyaminyl radical, which has been generated through the reductive intermolecular or intramolecular addition of carbon radicals to the carbon atom of oxime ethers (Friestad, 2001; Naito et al., 2000; Tauh & Fallis, 1999; Marco-Contelles et al., 1996; Enholm et al., 1990). We carried out this reaction by the intramolecular capture of an alkyl-oxyaminyl radical by a double bond in a cascade process yielding methyl 2-[(E)-1-(benzyloxyimino)ethyl]-5-bromo-2-cinnamylpent-4-enoate. This reaction involves two sequential 5-exo ring closures involving vinyl and neutral alkyl–oxyaminyl radicals, in a chain radical reaction, in which the attack of the radical is stereo-controlled by the the carboxymethyl group, and hence determining the stereochemistry of the new stereogenic bonds on the opposite face to that group.
The title molecule is shown in Fig. 1. There are no unusual bonds lengths or angles in the structure. The puckering of the two five-membered rings N1/C2/C3/C3A/C6A and C3A/C4/C5/C6/C6A as defined by the pseudorotation parameters P and τ(M), (Rao et al., 1981) are, for the former; P = 182.4 (1)°, τ(M) = 48.6 (1)°, reference bond N1—C2, corresponding to a twist on N1—C2 and for the latter; P = 340.4 (6)°, τ(M) = 12.2 (1)°, reference bond C3A—C4, corresponding to an envelope on C3A.
Two C—H···O hydrogen bonds are involved in the supramolecular stucture (Table 1). C5—H5···O1(1/2 + x, 1/2 − y, 1 − z) forms a C(6) chain (Fig. 2) (Bernstein et al., 1995) and C27—H27B···O32A forms aC(7) chain (Fig. 3), both of which run parallel to the a axis. The latter hydrogen bond links antiparallelC6 chains of the former type into a sheet consisting of a network of R44(24) rings which lies parallel to (010) (Fig 4). Atom C5 is a hydrogen donor to O1 in the molecule at (1/2 + x, 1/2 − y, 1 − z), Atom C27 in this molecule is a hydrogen donor to O1 in the molecule at (x, 1/2 − y, −1/2 − z), C27 in this molecule is a hydrogen donor to O32A in the molecule at (−1/2 + x, 1/2 − y, 1 − z), while C5 is a hydrogen donor to O32A in the molecule at (x, y, z). Two such sheets occur in the unit cell; one in the range 0.0 > y > 0.5 and 0.5 > y > 1.0. There are no interactions between adjacent sheets, C—H···π or π–π interactions being absent.