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_4519139
_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         'C26 H25 F N2 O5'
_chemical_formula_sum            'C26 H25 F N2 O5'
_chemical_formula_weight         464.48
_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             2020-07-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.577(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.7046(3)
_cell_length_b                   11.9983(4)
_cell_length_c                   11.5160(4)
_cell_measurement_reflns_used    7007
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      74.8770
_cell_measurement_theta_min      3.8850
_cell_volume                     1182.30(7)
_computing_cell_refinement       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_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 1.000
_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    145.00 177.00   1.00    1.00    --  106.49  57.00   0.00   32
  2  \w    100.00 129.00   1.00    1.00    --  106.49  57.00   0.00   29
  3  \w     36.00  81.00   1.00    0.10    --   48.45  38.00 120.00   45
  4  \w     85.00 117.00   1.00    0.10    --   48.45  38.00 120.00   32
  5  \w     68.00  94.00   1.00    0.10    --   48.45  19.00  71.00   26
  6  \w     98.00 126.00   1.00    1.00    --  106.49  19.00  71.00   28
  7  \w    100.00 133.00   1.00    1.00    --  106.49  38.00 -90.00   33
  8  \w     95.00 139.00   1.00    1.00    --  106.49  19.00-180.00   44
  9  \w     95.00 177.00   1.00    1.00    --  106.49  19.00-150.00   82
 10  \w    149.00 175.00   1.00    1.00    --  106.49  38.00 -90.00   26
 11  \w    128.00 153.00   1.00    1.00    --  106.49  19.00  71.00   25
 12  \w     38.00  92.00   1.00    1.00    --  106.49 -77.00 -30.00   54
 13  \w     36.00  63.00   1.00    1.00    --  106.49 -77.00  90.00   27
 14  \w     35.00  66.00   1.00    1.00    --  106.49 -57.00-180.00   31
 15  \w     72.00 102.00   1.00    1.00    --  106.49 -77.00  90.00   30
 16  \w     76.00 104.00   1.00    1.00    --  106.49 -77.00 150.00   28
 17  \w     38.00  69.00   1.00    1.00    --  106.49 -77.00 150.00   31
 18  \w     40.00  73.00   1.00    1.00    --  106.49 -99.00  90.00   33
 19  \w     77.00 104.00   1.00    1.00    --  106.49 -99.00  90.00   27
 20  \w     80.00 105.00   1.00    1.00    --  106.49 -99.00 150.00   25
 21  \w     34.00  60.00   1.00    1.00    --  106.49 -99.00 150.00   26
 22  \w    -15.00  26.00   1.00    0.10    --   48.45 -19.00 150.00   41
 23  \w    -21.00  10.00   1.00    0.10    --   48.45 -19.00 120.00   31
 24  \w    -12.00  22.00   1.00    0.10    --   48.45 -19.00 -96.00   34
 25  \w    -13.00  25.00   1.00    0.10    --  -48.45  19.00  71.00   38
 26  \w    -51.00 -16.00   1.00    1.00    --  -86.25  57.00 150.00   35
 27  \w    -63.00 -35.00   1.00    1.00    --  -86.25  57.00-150.00   28
 28  \w   -114.00 -86.00   1.00    0.10    --  -48.45 -19.00 -96.00   28
 29  \w   -120.00 -91.00   1.00    0.10    --  -48.45 -77.00-150.00   29
 30  \w    -83.00 -27.00   1.00    0.10    --  -48.45 -77.00-150.00   56
 31  \w    -81.00 -46.00   1.00    0.10    --  -48.45 -19.00 -96.00   35
 32  \w    -64.00 -26.00   1.00    0.10    --  -48.45 -77.00 150.00   38
 33  \w   -112.00 -74.00   1.00    1.00    --  -86.25 -19.00 -96.00   38
 34  \w    -92.00 -63.00   1.00    1.00    --  -86.25 -77.00-180.00   29
 35  \w    -91.00 -63.00   1.00    1.00    --  -86.25 -77.00-160.63   28
 36  \w   -103.00 -62.00   1.00    1.00    --  -86.25 -80.00-132.74   41
 37  \w   -159.00-122.00   1.00    1.00    --  -86.25 -77.00-180.00   37
 38  \w   -154.00-129.00   1.00    1.00    --  -86.25 -77.00-150.00   25
 39  \w   -154.00-115.00   1.00    1.00    --  -86.25 -77.00-160.63   39
 40  \w   -155.00-129.00   1.00    1.00    --  -86.25 -80.00-132.74   26
 41  \w   -158.00 -70.00   1.00    1.00    --  -86.25 -77.00-120.00   88
 42  \w   -104.00 -65.00   1.00    1.00    --  -86.25 -77.00-150.00   39
 43  \w   -159.00 -95.00   1.00    1.00    --  -86.25 -77.00 133.60   64
 44  \w    -91.00 -63.00   1.00    1.00    --  -86.25 -77.00 133.60   28
 45  \w    -88.00 -63.00   1.00    1.00    --  -86.25 -77.00 150.00   25
 46  \w    -91.00 -66.00   1.00    1.00    --  -86.25 -70.00 100.94   25
 47  \w   -111.00 -63.00   1.00    1.00    --  -86.25 -77.00 120.00   48
 48  \w   -159.00-122.00   1.00    1.00    --  -86.25 -77.00 120.00   37
 49  \w   -150.00-125.00   1.00    1.00    --  -86.25 -70.00 100.94   25
 50  \w   -136.00 -71.00   1.00    1.00    --  -86.25 -56.00 134.68   65
;
_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      0.1737961000
_diffrn_orient_matrix_UB_12      -0.0319922000
_diffrn_orient_matrix_UB_13      0.0345827000
_diffrn_orient_matrix_UB_21      0.0171368000
_diffrn_orient_matrix_UB_22      0.0072840000
_diffrn_orient_matrix_UB_23      -0.1305952000
_diffrn_orient_matrix_UB_31      0.0437237000
_diffrn_orient_matrix_UB_32      0.1241147000
_diffrn_orient_matrix_UB_33      0.0166762000
_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  0.0790
_diffrn_reflns_av_unetI/netI     0.0630
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            14443
_diffrn_reflns_point_group_measured_fraction_full 0.944
_diffrn_reflns_point_group_measured_fraction_max 0.957
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.028
_diffrn_reflns_theta_min         3.905
_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    0.798
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.36555
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.68a (Rigaku Oxford Diffraction, 2019)
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    1.305
_exptl_crystal_description       block
_exptl_crystal_F_000             488
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.457
_refine_diff_density_min         -0.241
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.0(4)
_refine_ls_extinction_coef       0.0058(14)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     308
_refine_ls_number_reflns         4045
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0744
_refine_ls_R_factor_gt           0.0663
_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^)+(0.0901P)^2^+0.1846P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1535
_refine_ls_wR_factor_ref         0.1627
_reflns_Friedel_coverage         0.820
_reflns_Friedel_fraction_full    0.897
_reflns_Friedel_fraction_max     0.911
_reflns_number_gt                3447
_reflns_number_total             4045
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c04460_si_002.cif
_cod_data_source_block           200718a
_cod_original_cell_volume        1182.30(6)
_cod_database_code               4519139
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         CNCl
_shelx_estimated_absorpt_t_max   0.984
_shelx_estimated_absorpt_t_min   0.969
_diffrn_oxdiff_digest_frames
;
012e5a22d560887cd9b5b12eaa18e43375018146869
;
_diffrn_oxdiff_digest_hkl
;
01fc218439343ff78793d95199f401788d2829
;
_reflns_odcompleteness_completeness 100.00
_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
2.a Ternary CH refined with riding coordinates:
 C11(H11), C16(H16), C23(H23)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C14(H14A,H14B), C15(H15A,H15B), C17(H17A,H17B), C18(H18A,
 H18B), C20(H20A,H20B), C21(H21A,H21B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C13(H13), C19(H19), C22(H22), C24(H24), C25(H25), C26(H26)
;
_shelx_res_checksum              21520
_shelx_hkl_checksum              65032
_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 1.881
_oxdiff_exptl_absorpt_empirical_full_min 0.517