Synthesis of Bis-pyrrolizidine-Fused Dispiro-oxindole Analogues of Curcumin via One-Pot Azomethine Ylide Cycloaddition: Experimental and Computational Approach toward Regio- and Diastereoselection.
Bharitkar, Yogesh P.; Das, Mohua; Kumari, Neha; Kumari, M. Padma; Hazra, Abhijit; Bhayye, Sagar S.; Natarajan, Ramalingam; Shah, Siddharth; Chatterjee, Sourav; Mondal, Nirup B.; Organic letters 17 (2015) 4440–4443; doi:10.1021/acs.orglett.5b02085

data_1534121
_publ_section_title
;
 Synthesis of Bis-pyrrolizidine-Fused Dispiro-oxindole Analogues of
 Curcumin via One-Pot Azomethine Ylide Cycloaddition: Experimental and
 Computational Approach toward Regio- and Diastereoselection.
;
_journal_issue                   18
_journal_name_full               'Organic letters'
_journal_page_first              4440
_journal_page_last               4443
_journal_paper_doi               10.1021/acs.orglett.5b02085
_journal_volume                  17
_journal_year                    2015
_chemical_formula_moiety         'C45 H42 I2 N4 O8'
_chemical_formula_sum            'C45 H42 I2 N4 O8'
_chemical_formula_weight         1020.62
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-01-13
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                90
_cell_angle_beta                 111.769(7)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   35.020(4)
_cell_length_b                   16.0741(18)
_cell_length_c                   20.002(3)
_cell_measurement_reflns_used    4526
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      16.146
_cell_measurement_theta_min      2.266
_cell_volume                     10456(2)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1494
_diffrn_reflns_av_unetI/netI     0.2184
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       45
_diffrn_reflns_limit_h_min       -44
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            61742
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.772
_diffrn_reflns_theta_min         1.252
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.250
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5288
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.1141 before and 0.0857 after correction.
The Ratio of minimum to maximum transmission is 0.7092.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.297
_exptl_crystal_description       needle
_exptl_crystal_F_000             4080
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.970
_refine_diff_density_min         -0.845
_refine_diff_density_rms         0.105
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.835
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     537
_refine_ls_number_reflns         11994
_refine_ls_number_restraints     72
_refine_ls_restrained_S_all      0.834
_refine_ls_R_factor_all          0.2643
_refine_ls_R_factor_gt           0.0822
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2268
_refine_ls_wR_factor_ref         0.3508
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3472
_reflns_number_total             11994
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5b02085_si_006.cif
_cod_data_source_block           CL_cy_4Bc_0m_a_sq
_cod_database_code               1534121
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 C35-C34 \\sim C34-C33 \\sim C33-C32 \\sim C37-C32 \\sim C37-C36
 with sigma of 0.02
3. Rigid bond restraints
 C33, C34, C35, C36, C37, C32, N1, C31, O3, C00Z
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim N1 \\sim C31 \\sim O3: within
1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
5.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3A), C8(H8), C25(H25), C26(H26), C27(H27)
5.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C28(H28A,H28B), C29(H29A,H29B),
 C30(H30A,H30B)
5.c Aromatic/amide H refined with riding coordinates:
 N1(H1A), N3(H3), C12(H12), C14(H14), C15(H15), C17(H17), C20(H20), C21(H21),
 C23(H23), C34(H34), C36(H36), C37(H37), C39(H39), C40(H40), C42(H42)
5.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C44(H44A,H44B,H44C)
5.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O4(H4), O7(H7)
;
_shelx_res_checksum              12129
_shelx_hkl_checksum              16944
_shelx_fab_checksum              51465
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'