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_1534119
_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 rmad
_chemical_formula_moiety         'C53 H45 N2 O8'
_chemical_formula_sum            'C53 H45 N2 O8'
_chemical_formula_weight         837.91
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-01-01
_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                   11.4428(7)
_cell_length_b                   15.4354(9)
_cell_length_c                   24.3994(15)
_cell_measurement_reflns_used    4814
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      19.51
_cell_measurement_theta_min      2.13
_cell_volume                     4309.5(5)
_computing_cell_refinement       'SAINT v7.34A (Bruker, 200?)'
_computing_data_reduction        'SAINT v7.34A (Bruker, 200?)'
_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 0.989
_diffrn_measured_fraction_theta_max 0.975
_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  0.0815
_diffrn_reflns_av_unetI/netI     0.0843
_diffrn_reflns_laue_measured_fraction_full 0.989
_diffrn_reflns_laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            40774
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.572
_diffrn_reflns_theta_min         1.966
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.087
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6451
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.1268 before and 0.0707 after correction.
The Ratio of minimum to maximum transmission is 0.8652.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.291
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1764
_exptl_crystal_size_max          0.43
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.28
_refine_diff_density_max         0.220
_refine_diff_density_min         -0.141
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 1645 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.7(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.986
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     573
_refine_ls_number_reflns         9668
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.986
_refine_ls_R_factor_all          0.1268
_refine_ls_R_factor_gt           0.0560
_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^)+(0.0642P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1210
_refine_ls_wR_factor_ref         0.1458
_reflns_Friedel_coverage         0.796
_reflns_friedel_fraction_full    0.983
_reflns_friedel_fraction_max     0.964
_reflns_number_gt                5129
_reflns_number_total             9668
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5b02085_si_008.cif
_cod_data_source_block           CL_cy_6a_0m_a
_cod_database_code               1534119
_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(H4), C5(H5), C29(H29), C30(H30), C31(H31)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), C32(H32A,H32B), C34(H34A,H34B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C12(H12), C13(H13), C14(H14), C18(H18), C19(H19), C20(H20), C22(H22),
 C23(H23), C26(H26), C33(H33), C38(H38), C39(H39), C40(H40), C44(H44), C45(H45),
  C46(H46), C48(H48), C49(H49), C52(H52)
2.d Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C53(H53A,H53B,H53C)
2.e Idealised tetrahedral OH refined as rotating group:
 O2(H2), O5(H5A), O7(H7)
;
_shelx_res_checksum              80074
_shelx_hkl_checksum              76233
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'