Reversal of enantioselective Friedel-Crafts C3-alkylation of pyrrole by slightly tuning the amide units of N,N'-dioxide ligands
Yulong Zhang; Na Yang; Xiaohua Liu; Jing Guo; Xiying Zhang; Lili Lin; Changwei Hu; Xiaoming Feng; Chem.Commun. 51 (2015) 8432–; doi:10.1039/C4cc10055G

data_7117140
_publ_section_title
;
 Reversal of enantioselective Friedel-Crafts C3-alkylation of pyrrole by
 slightly tuning the amide units of N,N'-dioxide ligands
;
_journal_name_full               Chem.Commun.
_journal_page_first              8432
_journal_paper_doi               10.1039/C4cc10055G
_journal_volume                  51
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C47 H76 N4 Ni O6, 2(C4 H8 O), 2(B F4)'
_chemical_formula_sum            'C55 H92 B2 F8 N4 Ni O8'
_chemical_formula_weight         1169.65
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'I 2y'
_space_group_name_H-M_alt        'I 1 2 1'
_symmetry_space_group_name_Hall  'I 2y'
_symmetry_space_group_name_H-M   'I 1 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_block_doi                 10.5517/cc13rz2x
_audit_creation_date             2015-01-12
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.09 svn.r3130 for OlexSys, GUI svn.r4987)
;
_audit_update_record
;
2015-01-13 deposited with the CCDC.
2015-02-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.682(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   16.4520(5)
_cell_length_b                   8.8684(3)
_cell_length_c                   22.2394(6)
_cell_measurement_reflns_used    5477
_cell_measurement_temperature    112(3)
_cell_measurement_theta_max      72.5710
_cell_measurement_theta_min      4.2530
_cell_volume                     3035.68(17)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_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_environment      N~2~
_diffrn_ambient_temperature      112(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega    1.00   75.00   1.0000    4.6800
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -99.0000   30.0000 74

  2 omega   10.00  104.00   1.0000    4.6800
omega____ theta____ kappa____ phi______ frames
    -       36.2921   77.0000  120.0000 94

  3 omega  -33.00   55.00   1.0000    4.6800
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -38.0000   60.0000 88

  4 omega   20.00  104.00   1.0000    4.6800
omega____ theta____ kappa____ phi______ frames
    -       36.2921   57.0000  -30.0000 84

  5 omega   23.00   90.00   1.0000    4.6800
omega____ theta____ kappa____ phi______ frames
    -       36.2921 -125.0000  -60.0000 67

  6 omega   38.00   91.00   1.0000   18.7000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -30.0000 53

  7 omega   39.00  109.00   1.0000   18.7000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000 -120.0000 70

  8 omega   38.00   91.00   1.0000   18.7000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000   30.0000 53

  9 omega   91.00  176.00   1.0000   18.7000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000    0.0000 85

 10 omega   38.00   91.00   1.0000   18.7000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -150.0000 53

 11 omega   91.00  176.00   1.0000   18.7000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000   90.0000 85

 12 omega   38.00   91.00   1.0000   18.7000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -120.0000 53

 13 omega   39.00  109.00   1.0000   18.7000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000   90.0000 70

 14 omega   40.00  135.00   1.0000   18.7000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000  -90.0000 95

 15 omega   17.00  105.00   1.0000    4.6800
omega____ theta____ kappa____ phi______ frames
    -       36.2921   38.0000 -120.0000 88

 16 omega  -31.00   53.00   1.0000    4.6800
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -57.0000 -180.0000 84

 17 omega  -31.00   53.00   1.0000    4.6800
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -57.0000  -90.0000 84

 18 omega   20.00  104.00   1.0000    4.6800
omega____ theta____ kappa____ phi______ frames
    -       36.2921   57.0000   60.0000 84

 19 omega   70.00  158.00   1.0000   18.7000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000 -120.0000 88

 20 omega   90.00  175.00   1.0000   18.7000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  -60.0000 85
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0261263000
_diffrn_orient_matrix_UB_12      -0.0811403000
_diffrn_orient_matrix_UB_13      0.0653350000
_diffrn_orient_matrix_UB_21      0.0876105000
_diffrn_orient_matrix_UB_22      -0.0442662000
_diffrn_orient_matrix_UB_23      -0.0055880000
_diffrn_orient_matrix_UB_31      0.0407420000
_diffrn_orient_matrix_UB_32      0.1471319000
_diffrn_orient_matrix_UB_33      0.0343506000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0310
_diffrn_reflns_av_unetI/netI     0.0361
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            10156
_diffrn_reflns_point_group_measured_fraction_full 0.849
_diffrn_reflns_point_group_measured_fraction_max 0.849
_diffrn_reflns_theta_full        67.074
_diffrn_reflns_theta_max         67.074
_diffrn_reflns_theta_min         5.422
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.117
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48655
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.280
_exptl_crystal_F_000             1248
_exptl_crystal_size_max          0.7
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.476
_refine_diff_density_min         -0.435
_refine_diff_density_rms         0.064
_refine_ls_abs_structure_details
;
 Flack x determined using 1622 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.004(17)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     360
_refine_ls_number_reflns         4627
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0480
_refine_ls_R_factor_gt           0.0470
_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^)+(0.0922P)^2^+1.0234P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1227
_refine_ls_wR_factor_ref         0.1244
_reflns_Friedel_coverage         0.589
_reflns_Friedel_fraction_full    0.678
_reflns_Friedel_fraction_max     0.678
_reflns_number_gt                4495
_reflns_number_total             4627
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4cc10055g2.cif
_cod_data_source_block           1a
_cod_original_cell_volume        3035.68(16)
_cod_database_code               7117140
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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,H) groups
2. Others
 Fixed Sof: H24A(0.5) H24B(0.5)
3.a Rotating group:
 OW1(HW1A,HW1B)
3.b Ternary CH refined with riding coordinates:
 C16(H16), C18(H18), C22(H22)
3.c Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B), C23(H23A,
 H23B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B),
 C28(H28A,H28B)
3.d Aromatic/amide H refined with riding coordinates:
 N2(H2), C9(H9), C11(H11), C13(H13)
3.e Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C6(H6A,
 H6B,H6C), C7(H7A,H7B,H7C)
;
_shelx_res_checksum              12183
_shelx_hkl_checksum              40528
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'