Highly Enantioselective Copper- and Iron-Catalyzed Intramolecular Cyclopropanation of Indoles.
Xu, Huan; Li, Yi-Pan; Cai, Yan; Wang, Guo-Peng; Zhu, Shou-Fei; Zhou, Qi-Lin; Journal of the American Chemical Society 139 (2017) 7697–7700; doi:10.1021/jacs.7b03086

data_4131290
_publ_section_title
;
 Highly Enantioselective Copper- and Iron-Catalyzed Intramolecular
 Cyclopropanation of Indoles.
;
_journal_issue                   23
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              7697
_journal_page_last               7700
_journal_paper_doi               10.1021/jacs.7b03086
_journal_volume                  139
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H23 I N2 O2'
_chemical_formula_sum            'C25 H23 I N2 O2'
_chemical_formula_weight         510.35
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2016-02-29
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.0754(17)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.04752(15)
_cell_length_b                   8.79412(14)
_cell_length_c                   15.1588(3)
_cell_measurement_reflns_used    11349
_cell_measurement_temperature    113(2)
_cell_measurement_theta_max      31.0960
_cell_measurement_theta_min      2.3140
_cell_volume                     1064.63(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrystalClear-SM Expert 2.1 b42 (Rigaku, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      113.15
_diffrn_detector                 PILT
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.884
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w   -105.00  75.00   0.50   10.00    --  -15.00  45.00   0.00  360
  2  \w   -105.00  75.00   0.50   10.00    --  -15.00  45.00  90.00  360
  3  \w   -105.00  75.00   0.50   10.00    --  -15.00  45.00 180.00  360
;
_diffrn_measurement_device       'Rigaku Xtalab P200'
_diffrn_measurement_device_type  'Rigaku Xtalab P200'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0053004000
_diffrn_orient_matrix_UB_12      0.0784338000
_diffrn_orient_matrix_UB_13      0.0106506000
_diffrn_orient_matrix_UB_21      -0.0244595000
_diffrn_orient_matrix_UB_22      0.0186331000
_diffrn_orient_matrix_UB_23      -0.0453361000
_diffrn_orient_matrix_UB_31      -0.0851862000
_diffrn_orient_matrix_UB_32      -0.0004456000
_diffrn_orient_matrix_UB_33      0.0076132000
_diffrn_radiation_monochromator  confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0346
_diffrn_reflns_av_unetI/netI     0.0237
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.884
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            12569
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.833
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         31.029
_diffrn_reflns_theta_min         2.550
_diffrn_source                   'rotating anode'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.528
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79146
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.592
_exptl_crystal_description       plate
_exptl_crystal_F_000             512
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.14
_refine_diff_density_max         1.042
_refine_diff_density_min         -1.458
_refine_diff_density_rms         0.093
_refine_ls_abs_structure_details
;
 Flack x determined using 2397 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.031(18)
_refine_ls_extinction_coef       0.0075(14)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/8 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     280
_refine_ls_number_reflns         5673
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0359
_refine_ls_R_factor_gt           0.0351
_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^)+(0.0490P)^2^+1.3280P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0904
_refine_ls_wR_factor_ref         0.0915
_reflns_Friedel_coverage         0.779
_reflns_Friedel_fraction_full    0.965
_reflns_Friedel_fraction_max     0.775
_reflns_number_gt                5576
_reflns_number_total             5673
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            13-cif.cif
_cod_data_source_block           m2016023b
_cod_database_code               4131290
_chemical_oxdiff_formula         C25H23N2O2I
_shelx_estimated_absorpt_t_max   0.814
_shelx_estimated_absorpt_t_min   0.711
_reflns_odcompleteness_completeness 88.42
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.96
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C1(H1), C3(H3)
2.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B), C19(H19A,H19B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C15(H15), C16(H16), C17(H17), C18(H18),
 C21(H21), C22(H22), C23(H23), C24(H24), C25(H25)
;
_shelx_res_checksum              34886
_shelx_hkl_checksum              63313
_shelx_shelxl_version_number     2014/8
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 4.710
_oxdiff_exptl_absorpt_empirical_full_min 0.630