Enantioselective Construction of Spiro[indoline-3,2'-pyrrole] Framework via Catalytic Asymmetric 1,3-Dipolar Cycloadditions Using Allenes as Equivalents of Alkynes.
Wang, Cong-Shuai; Zhu, Ren-Yi; Zheng, Jian; Shi, Feng; Tu, Shu-Jiang; The Journal of organic chemistry 80 (2014) 512–; doi:10.1021/jo502516e

data_4030387
_publ_section_title
;
 Enantioselective Construction of Spiro[indoline-3,2'-pyrrole] Framework
 via Catalytic Asymmetric 1,3-Dipolar Cycloadditions Using Allenes as
 Equivalents of Alkynes.
;
_journal_issue                   1
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              512
_journal_paper_doi               10.1021/jo502516e
_journal_volume                  80
_journal_year                    2014
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C41 H35 Br N2 O7'
_chemical_formula_sum            'C41 H35 Br N2 O7'
_chemical_formula_weight         747.62
_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             2014-08-25
_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                   7.3188(7)
_cell_length_b                   21.396(2)
_cell_length_c                   22.175(2)
_cell_measurement_reflns_used    3023
_cell_measurement_temperature    130
_cell_measurement_theta_max      31.2201
_cell_measurement_theta_min      2.65
_cell_volume                     3472.5(6)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2007)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution
;
????
;
_diffrn_ambient_temperature      130
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
scan:
    Number of images: 340
               Slice: -110.0000 - 60.0000
         Image width: 0.5000
            Exp time: 16.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 270.0000
                 XTD: 45.3038
              2theta: -20.1830
;
_diffrn_measurement_device
;
Saturn724+ (2x2 bin mode)
;
_diffrn_measurement_device_details
;
AFC10: Fixed Chi 2 circle
;
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_orient_matrix_type       d*Trek
_diffrn_orient_matrix_UB_11      -0.0416
_diffrn_orient_matrix_UB_12      -0.0191
_diffrn_orient_matrix_UB_13      0.0361
_diffrn_orient_matrix_UB_21      0.0301
_diffrn_orient_matrix_UB_22      -0.0492
_diffrn_orient_matrix_UB_23      0.0086
_diffrn_orient_matrix_UB_31      0.0196
_diffrn_orient_matrix_UB_32      0.0176
_diffrn_orient_matrix_UB_33      0.0318
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1099
_diffrn_reflns_av_unetI/netI     0.1527
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            35305
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.575
_diffrn_reflns_theta_min         1.323
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           24.0000
_diffrn_source_power             1.2000
_diffrn_source_voltage           50.0000
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.240
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.1631
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.430
_exptl_crystal_description       block
_exptl_crystal_F_000             1544
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.471
_refine_diff_density_min         -0.477
_refine_diff_density_rms         0.067
_refine_ls_abs_structure_details
;
 Flack x determined using 1567 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.022(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.967
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     463
_refine_ls_number_reflns         10632
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      0.974
_refine_ls_R_factor_all          0.1700
_refine_ls_R_factor_gt           0.0620
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0470P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1046
_refine_ls_wR_factor_ref         0.1354
_reflns_Friedel_coverage         0.788
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                5096
_reflns_number_total             10632
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo502516e_si_002.cif
_cod_data_source_block           sf140825
_cod_depositor_comments          'Adding full bibliography for 4030387.cif.'
_cod_original_cell_volume        3472.4(6)
_cod_database_code               4030387
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.964
_shelx_estimated_absorpt_t_min   0.866
_diffrn_number_total             2330
_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
2. Uiso/Uaniso restraints and constraints
O7 \\sim C30 \\sim C31: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C31) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
3.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C30(H30A,H30B), C33(H33A,H33B), C35(H35A,H35B)
3.b Aromatic/amide H refined with riding coordinates:
 N2(H2), C4(H4), C5(H5), C6(H6), C7(H7), C16(H16), C17(H17), C18(H18),
 C19(H19), C21(H21), C23(H23), C24(H24), C25(H25), C26(H26), C37(H37), C38(H38),
  C40(H40), C41(H41)
3.c Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C31(H31A,H31B,H31C), C34(H34A,H34B,H34C)
;
_shelx_res_checksum              53702
_shelx_hkl_checksum              47622
_olex2_submission_special_instructions 'No special instructions were received'