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_1534120
_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_absolute_configuration syn
_chemical_formula_moiety         'C47 H48 N4 O8, C H4 O'
_chemical_formula_sum            'C48 H52 N4 O9'
_chemical_formula_weight         828.93
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_symmetry_space_group_name_Hall  'P 2 2ab'
_symmetry_space_group_name_H-M   'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2014-12-26
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.958(2)
_cell_length_b                   25.526(4)
_cell_length_c                   11.093(2)
_cell_measurement_reflns_used    1223
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      18.39
_cell_measurement_theta_min      2.43
_cell_volume                     4235.5(12)
_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)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.992
_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  0.1959
_diffrn_reflns_av_unetI/netI     0.2638
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            35476
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.470
_diffrn_reflns_theta_min         1.578
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.090
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6314
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.1401 before and 0.0783 after correction.
The Ratio of minimum to maximum transmission is 0.8468.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.300
_exptl_crystal_description       block
_exptl_crystal_F_000             1760
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.21
_refine_diff_density_max         0.242
_refine_diff_density_min         -0.252
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
;
 Flack x determined using 906 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.4(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.898
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     559
_refine_ls_number_reflns         9607
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.898
_refine_ls_R_factor_all          0.2581
_refine_ls_R_factor_gt           0.0681
_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^)+(0.0580P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1272
_refine_ls_wR_factor_ref         0.1914
_reflns_Friedel_coverage         0.798
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                3149
_reflns_number_total             9607
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5b02085_si_005.cif
_cod_data_source_block           CL_cy_4Gb_a
_cod_original_cell_volume        4235.7(13)
_cod_database_code               1534120
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C3(H3), C4(H4A), C5(H5), C27(H27), C28(H28), C29(H29)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), C30(H30A,H30B), C31(H31A,H31B),
 C32(H32A,H32B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1A), C13(H13), C14(H14), C15(H15), C16(H16), C20(H20), C21(H21), C24(H24),
  C35(H35), C36(H36), C37(H37), C38(H38), C42(H42), C43(H43), C46(H46)
2.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C25(H25A,H25B,H25C), C40(H40A,H40B,H40C), C47(H47A,H47B,
 H47C), C48(H48A,H48B,H48C)
2.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O4(H4), O7(H7), O9(H9)
;
_shelx_res_checksum              37265
_shelx_hkl_checksum              69984
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'