Ni(II)-Catalyzed Asymmetric Nitration of Oxindoles: Construction of Cipargamin Analogues
Lv, Mingjun; Li, Xiaoxun; ACS Catalysis  (2021) 14829–14835; doi:10.1021/acscatal.1c04460

data_4519140
_publ_section_title
;
 Ni(II)-Catalyzed Asymmetric Nitration of Oxindoles: Construction of
 Cipargamin Analogues
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              14829
_journal_page_last               14835
_journal_paper_doi               10.1021/acscatal.1c04460
_journal_year                    2021
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C19 H15 Cl2 N3 O, C3 H8 O'
_chemical_formula_sum            'C22 H23 Cl2 N3 O2'
_chemical_formula_weight         432.33
_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   geom
_audit_creation_date             2021-01-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 104.962(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.7747(3)
_cell_length_b                   7.5306(3)
_cell_length_c                   14.5872(4)
_cell_measurement_reflns_used    4463
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      74.2330
_cell_measurement_theta_min      3.1140
_cell_volume                     1037.35(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.999
_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     97.00 149.00   1.00    0.31    --  106.49  77.00 -90.00   52
  2  \w    153.00 178.00   1.00    0.31    --  106.49  77.00 -90.00   25
  3  \w     95.00 176.00   1.00    0.31    --  106.49  26.00-121.00   81
  4  \w     56.00  89.00   1.00    0.10    --   48.32  26.00-121.00   33
  5  \w    -25.00  24.00   1.00    0.10    --   48.32 -19.00 -60.00   49
  6  \w     37.00  68.00   1.00    0.31    --  106.49 -77.00-180.00   31
  7  \w     72.00 102.00   1.00    0.31    --  106.49 -77.00-180.00   30
  8  \w     40.00  66.00   1.00    0.31    --  106.49 -57.00 -60.00   26
  9  \w     -5.00  24.00   1.00    0.10    --   48.32 -26.00  75.00   29
 10  \w     34.00  63.00   1.00    0.31    --  106.49 -57.00 150.00   29
 11  \w    129.00 165.00   1.00    0.31    --  106.49 125.00  60.00   36
 12  \w     95.00 127.00   1.00    0.31    --  106.49 125.00  60.00   32
 13  \w     95.00 177.00   1.00    0.31    --  106.49 125.00 -90.00   82
 14  \w     37.00  63.00   1.00    0.31    --  106.49-125.00 -60.00   26
 15  \w     65.00 111.00   1.00    0.31    --  106.49-125.00 -60.00   46
 16  \w    -31.00  26.00   1.00    0.10    --  -48.32  26.00-121.00   57
 17  \w    -65.00 -14.00   1.00    0.31    --  -86.25  57.00 -60.00   51
 18  \w    -66.00 -14.00   1.00    0.31    --  -86.25  57.00  30.00   52
 19  \w    -38.00 -13.00   1.00    0.31    --  -86.25  38.00  60.00   25
 20  \w   -120.00 -37.00   1.00    0.10    --  -48.32 -26.00  75.00   83
 21  \w    -65.00 -26.00   1.00    0.10    --  -48.32 -77.00   0.00   39
 22  \w    -62.00 -28.00   1.00    0.10    --  -48.32 -77.00 -60.00   34
 23  \w   -106.00 -80.00   1.00    0.10    --  -48.32 -77.00   0.00   26
 24  \w   -152.00-127.00   1.00    0.31    --  -86.25 -80.00 -12.87   25
 25  \w   -159.00-120.00   1.00    0.31    --  -86.25 -77.00 -60.00   39
 26  \w   -118.00 -62.00   1.00    0.31    --  -86.25 -80.00 -12.87   56
 27  \w    -88.00 -63.00   1.00    0.31    --  -86.25 -77.00  30.00   25
 28  \w   -130.00 -62.00   1.00    0.31    --  -86.25 -80.00  17.72   68
 29  \w   -148.00-110.00   1.00    0.31    --  -86.25 -77.00  30.00   38
 30  \w   -122.00 -63.00   1.00    0.31    --  -86.25 -77.00   0.00   59
 31  \w   -107.00 -63.00   1.00    0.31    --  -86.25 -77.00 -60.00   44
 32  \w   -107.00 -64.00   1.00    0.31    --  -86.25 -76.00 -39.19   43
 33  \w   -148.00-122.00   1.00    0.31    --  -86.25 -76.00 -39.19   26
 34  \w   -151.00 -67.00   1.00    0.31    --  -86.25 -74.00  47.36   84
 35  \w   -131.00-106.00   1.00    0.31    --  -86.25 -26.00  75.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1098427000
_diffrn_orient_matrix_UB_12      0.0637906000
_diffrn_orient_matrix_UB_13      0.0897962000
_diffrn_orient_matrix_UB_21      0.1189726000
_diffrn_orient_matrix_UB_22      -0.0261891000
_diffrn_orient_matrix_UB_23      -0.0504319000
_diffrn_orient_matrix_UB_31      -0.0202497000
_diffrn_orient_matrix_UB_32      0.1925398000
_diffrn_orient_matrix_UB_33      -0.0366470000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0596
_diffrn_reflns_av_unetI/netI     0.0580
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            10652
_diffrn_reflns_point_group_measured_fraction_full 0.968
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.080
_diffrn_reflns_theta_min         3.136
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    3.008
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.50893
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.384
_exptl_crystal_description       block
_exptl_crystal_F_000             452
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.252
_refine_diff_density_min         -0.298
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details
;
 Flack x determined using 1284 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.017(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     274
_refine_ls_number_reflns         3632
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0492
_refine_ls_R_factor_gt           0.0426
_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^)+(0.0640P)^2^+0.0230P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1110
_refine_ls_wR_factor_ref         0.1158
_reflns_Friedel_coverage         0.814
_reflns_Friedel_fraction_full    0.948
_reflns_Friedel_fraction_max     0.962
_reflns_number_gt                3214
_reflns_number_total             3632
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c04460_si_003.cif
_cod_data_source_block           210126c
_cod_database_code               4519140
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         ClC
_shelx_estimated_absorpt_t_max   0.864
_shelx_estimated_absorpt_t_min   0.840
_diffrn_oxdiff_digest_frames
;
01e8fa6637855b6523f2b725722352502301506717f
;
_diffrn_oxdiff_digest_hkl
;
0107d27859b773b68d32b93e2e8cc2fec01105
;
_reflns_odcompleteness_completeness 99.90
_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 C(H,H,H,H,H,H) groups, All O(H,H) groups
2. Others
 Fixed Sof: H0A(0.6) H0AA(0.4) C1(0.6) H1A(0.6) C1A(0.4) H1AA(0.4) H2AA(0.6)
 H2AB(0.6) H2AC(0.6) H2BD(0.4) H2BE(0.4) H2BF(0.4) H3AA(0.6) H3AB(0.6)
 H3AC(0.6) H3BD(0.4) H3BE(0.4) H3BF(0.4)
3.a Ternary CH refined with riding coordinates:
 C15(H15), C1(H1A), C1A(H1AA)
3.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B)
3.c Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2), N3(H3), C4(H4), C6(H6), C9(H9), C19(H19), C20(H20), C22(H22)
3.d Tetrahedral OH refined with riding coordinates:
 O0A(H0A), O0A(H0AA)
3.e Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C2(H2AA,H2AB,H2AC), C2(H2BD,H2BE,H2BF), C3(H3AA,H3AB,
 H3AC), C3(H3BD,H3BE,H3BF)
;
_shelx_res_checksum              72722
_shelx_hkl_checksum              13880
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 3.037
_oxdiff_exptl_absorpt_empirical_full_min 0.446