Chiral Nickel(II) Complex Catalyzed Enantioselective Doyle-Kirmse Reaction of α-Diazo Pyrazoleamides.
Lin, Xiaobin; Tang, Yu; Yang, Wei; Tan, Fei; Lin, Lili; Liu, Xiaohua; Feng, Xiaoming; Journal of the American Chemical Society 140 (2018) 3299–3305; doi:10.1021/jacs.7b12486

data_4131890
_publ_section_title
;
 Chiral Nickel(II) Complex Catalyzed Enantioselective Doyle-Kirmse
 Reaction of \a-Diazo Pyrazoleamides.
;
_journal_issue                   9
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              3299
_journal_page_last               3305
_journal_paper_doi               10.1021/jacs.7b12486
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C42 H68 N4 Ni O6, C46 H74 N4 Ni O6'
_chemical_formula_sum            'C88 H142 N8 Ni2 O12'
_chemical_formula_weight         1621.51
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2017-11-22
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.962(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.9543(2)
_cell_length_b                   23.5971(6)
_cell_length_c                   20.4838(6)
_cell_measurement_reflns_used    15145
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      68.4950
_cell_measurement_theta_min      4.3200
_cell_volume                     5266.2(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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 (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      150(2)
_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  -31.00   63.00   1.0000    4.0200
omega____ theta____ kappa____ phi______ frames
    -       36.1671  -77.0000   30.0000 94

  2 omega    9.00  104.00   1.0000    4.0200
omega____ theta____ kappa____ phi______ frames
    -       36.1671   77.0000  150.0000 95

  3 omega    1.00   75.00   1.0000    4.0200
omega____ theta____ kappa____ phi______ frames
    -       36.1671  -99.0000 -180.0000 74

  4 omega  -31.00   53.00   1.0000    4.0200
omega____ theta____ kappa____ phi______ frames
    -       36.1671  -57.0000  -90.0000 84

  5 omega  -31.00   53.00   1.0000    4.0200
omega____ theta____ kappa____ phi______ frames
    -       36.1671  -57.0000  150.0000 84

  6 omega   23.00   90.00   1.0000    4.0200
omega____ theta____ kappa____ phi______ frames
    -       36.1671 -125.0000  -90.0000 67

  7 omega  -31.00   53.00   1.0000    4.0200
omega____ theta____ kappa____ phi______ frames
    -       36.1671  -57.0000   60.0000 84

  8 omega    1.00   75.00   1.0000    4.0200
omega____ theta____ kappa____ phi______ frames
    -       36.1671  -99.0000  -60.0000 74

  9 omega    7.00  108.00   1.0000    4.0200
omega____ theta____ kappa____ phi______ frames
    -       36.1671   19.0000  -30.0000 101

 10 omega    9.00  104.00   1.0000    4.0200
omega____ theta____ kappa____ phi______ frames
    -       36.1671   77.0000  -90.0000 95

 11 omega   19.00  103.00   1.0000    4.0200
omega____ theta____ kappa____ phi______ frames
    -       36.1671   57.0000  -30.0000 84

 12 omega   40.00   98.00   1.0000   16.0700
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  -60.0000 58

 13 omega   39.00  109.00   1.0000   16.0700
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  120.0000 70

 14 omega   37.00  146.00   1.0000   16.0700
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -15.0000   30.0000 109

 15 omega   38.00   91.00   1.0000   16.0700
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -180.0000 53

 16 omega   39.00  109.00   1.0000   16.0700
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  -30.0000 70

 17 omega   38.00  116.00   1.0000   16.0700
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  -90.0000 78

 18 omega   39.00  109.00   1.0000   16.0700
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000   30.0000 70

 19 omega   40.00   98.00   1.0000   16.0700
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000    0.0000 58

 20 omega   40.00   98.00   1.0000   16.0700
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  150.0000 58

 21 omega   40.00  135.00   1.0000   16.0700
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000 -180.0000 95

 22 omega   91.00  176.00   1.0000   16.0700
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000  -30.0000 85

 23 omega   40.00   98.00   1.0000   16.0700
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000 -120.0000 58

 24 omega   38.00   91.00   1.0000   16.0700
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000   90.0000 53

 25 omega   39.00  177.00   1.0000   16.0700
omega____ theta____ kappa____ phi______ frames
    -      108.0000    0.0000  120.0000 138

 26 omega   38.00   91.00   1.0000   16.0700
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -120.0000 53

 27 omega   41.00  126.00   1.0000   16.0700
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -61.0000   60.0000 85

 28 omega    9.00  104.00   1.0000    4.0200
omega____ theta____ kappa____ phi______ frames
    -       36.1671   77.0000   90.0000 95

 29 omega   19.00  103.00   1.0000    4.0200
omega____ theta____ kappa____ phi______ frames
    -       36.1671   57.0000 -120.0000 84

 30 omega    9.00  104.00   1.0000    4.0200
omega____ theta____ kappa____ phi______ frames
    -       36.1671   77.0000    0.0000 95

 31 omega   19.00  103.00   1.0000    4.0200
omega____ theta____ kappa____ phi______ frames
    -       36.1671   57.0000   60.0000 84
;
_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      -0.0376998000
_diffrn_orient_matrix_UB_12      -0.0612442000
_diffrn_orient_matrix_UB_13      -0.0187103000
_diffrn_orient_matrix_UB_21      0.0157955000
_diffrn_orient_matrix_UB_22      0.0129388000
_diffrn_orient_matrix_UB_23      -0.0723717000
_diffrn_orient_matrix_UB_31      0.1353223000
_diffrn_orient_matrix_UB_32      -0.0186016000
_diffrn_orient_matrix_UB_33      0.0114329000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0393
_diffrn_reflns_av_unetI/netI     0.0392
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            55612
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.079
_diffrn_reflns_theta_max         67.079
_diffrn_reflns_theta_min         4.330
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.857
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51646
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.023
_exptl_crystal_description       block
_exptl_crystal_F_000             1756
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.26
_refine_diff_density_max         0.430
_refine_diff_density_min         -0.270
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 4574 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.066(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     924
_refine_ls_number_reflns         18807
_refine_ls_number_restraints     11
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0951
_refine_ls_R_factor_gt           0.0699
_refine_ls_shift/su_max          0.197
_refine_ls_shift/su_mean         0.004
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1153P)^2^+0.8148P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1958
_refine_ls_wR_factor_ref         0.2174
_reflns_Friedel_coverage         0.948
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                13001
_reflns_number_total             18807
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b12486_si_001.cif
_cod_data_source_block           1
_cod_database_code               4131890
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.808
_shelx_estimated_absorpt_t_min   0.759
_reflns_odcompleteness_completeness 99.93
_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. Restrained distances
 C42-C41
 1.5 with sigma of 0.01
 C34-C33
 1.5 with sigma of 0.01
 C75-C77
 1.5 with sigma of 0.01
3. Rigid bond restraints
 C71, C72
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C17 \\sim C18: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
5.a Riding coordinates:
 O6(H6A,H6B)
5.b Ternary CH refined with riding coordinates:
 C3(H3), C10(H10), C14(H14), C25(H25), C33(H33), C36(H36), C45(H45), C52(H52),
 C56(H56), C67(H67), C75(H75), C78(H78)
5.c Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,
 H19B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B),
 C24(H24A,H24B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B), C42(H42A,H42B),
  C57(H57A,H57B), C58(H58A,H58B), C59(H59A,H59B), C60(H60A,H60B), C61(H61A,
 H61B), C62(H62A,H62B), C63(H63A,H63B), C64(H64A,H64B), C65(H65A,H65B),
 C66(H66A,H66B), C81(H81A,H81B), C82(H82A,H82B), C83(H83A,H83B), C84(H84A,H84B),
  C85(H85A,H85B), C86(H86A,H86B), C87(H87A,H87B), C88(H88A,H88B)
5.d Aromatic/amide H refined with riding coordinates:
 N1(H1), N4(H4), C5(H5A), C6(H6), C7(H7), C31(H31), C30(H30), C29(H29), N5(H5),
  N8(H8), C47(H47), C48(H48), C49(H49), C73(H73), C72(H72), C71(H71)
5.e Fitted hexagon refined as free rotating group:
 C9(C4,C5,C6,C7,C8), C27(C32,C31,C30,C29,C28), C51(C46,C47,C48,C49,C50),
 C69(C74,C73,C72,C71,C70)
5.f Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C),
 C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C37(H37A,H37B,H37C), C38(H38A,H38B,
 H38C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C53(H53A,H53B,H53C), C54(H54A,
 H54B,H54C), C76(H76A,H76B,H76C), C77(H77A,H77B,H77C), C79(H79A,H79B,H79C),
 C80(H80A,H80B,H80C)
;
_olex2_submission_special_instructions 'No special instructions were received'