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_1534122
_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         'C49 H52 N4 O8, 2(C5 H5 N)'
_chemical_formula_sum            'C59 H63 N6 O8'
_chemical_formula_weight         984.15
_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             2015-07-01
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 120.843(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.0623(18)
_cell_length_b                   15.4284(14)
_cell_length_c                   19.2848(17)
_cell_measurement_reflns_used    2683
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      21.056
_cell_measurement_theta_min      2.365
_cell_volume                     5125.0(8)
_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, 2015)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_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  0.0838
_diffrn_reflns_av_unetI/netI     0.0766
_diffrn_reflns_laue_measured_fraction_full 0.991
_diffrn_reflns_laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            27998
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.081
_diffrn_reflns_theta_max         25.081
_diffrn_reflns_theta_min         1.778
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.085
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6677
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.1400 before and 0.0650 after correction.
The Ratio of minimum to maximum transmission is 0.8960.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.275
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2092
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.174
_refine_diff_density_min         -0.182
_refine_diff_density_rms         0.043
_refine_ls_extinction_coef       0.0014(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   0.966
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     337
_refine_ls_number_reflns         4520
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.966
_refine_ls_R_factor_all          0.1188
_refine_ls_R_factor_gt           0.0507
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0698P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1179
_refine_ls_wR_factor_ref         0.1471
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2388
_reflns_number_total             4520
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5b02085_si_004.cif
_cod_data_source_block           CL_cy_4Fb_0m_a
_cod_database_code               1534122
_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. Others
 Fixed Sof: H1(0.5)
3.a Ternary CH refined with riding coordinates:
 C3(H3A), C4(H4), C5(H5)
3.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B)
3.c Aromatic/amide H refined with riding coordinates:
 N1(H1A), C1(H1B), C13(H13), C15(H15), C19(H19), C20(H20), C23(H23), C26(H26),
 C27(H27), C28(H28), C29(H29), C30(H30)
3.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C)
3.e Idealised tetrahedral OH refined as rotating group:
 O1(H1)
3.f Idealised tetrahedral OH refined as rotating group with stretchable bonds:
 O3(H3)
;
_shelx_res_checksum              53737
_shelx_hkl_checksum              79841
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'