Py-2NO ligand enabled Ni(ii)-catalyzed asymmetric Michael addition reaction of indoles with β,γ-unsaturated α-keto esters
Chen, Zi-Yue; Wang, Xi-Rui; Xu, Ke-Lan; Hu, Pan; Tian, You-Ping; Wang, Hui-Juan; Zhou, Ying; Liu, Xiong-Li; New Journal of Chemistry 48 (2024) 1688–1695; doi:10.1039/D3NJ05076A

data_7062948
_publ_section_title
;
 Py-2NO ligand enabled Ni(ii)-catalyzed asymmetric Michael addition
 reaction of indoles with \b,\g-unsaturated \a-keto esters
;
_journal_issue                   4
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              1688
_journal_page_last               1695
_journal_paper_doi               10.1039/D3NJ05076A
_journal_volume                  48
_journal_year                    2024
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C23 H29 N3 O4'
_chemical_formula_sum            'C23 H29 N3 O4'
_chemical_formula_weight         411.49
_space_group_crystal_system      hexagonal
_space_group_IT_number           169
_space_group_name_Hall           'P 61'
_space_group_name_H-M_alt        'P 61'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2023-11-03
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2023-11-03 deposited with the CCDC.	2023-12-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            12
_cell_length_a                   25.6308(19)
_cell_length_b                   25.6308(19)
_cell_length_c                   13.8132(12)
_cell_measurement_reflns_used    4076
_cell_measurement_temperature    170.00(10)
_cell_measurement_theta_max      66.1260
_cell_measurement_theta_min      3.4170
_cell_volume                     7858.7(11)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      170.00(10)
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.973
_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    -36.00 -10.00   1.00   10.00    --  -41.11 -77.00-120.00   26
  2  \w   -116.00 -90.00   1.00   10.00    --  -41.11 -77.00-120.00   26
  3  \w    -63.00 -17.00   1.00   10.00    --  -41.11 -38.00 -60.00   46
  4  \w    -52.00 -23.00   1.00   10.00    --  -41.11 -57.00   0.00   29
  5  \w    -68.00  32.00   1.00   10.00    --  -41.11  57.00   0.00  100
  6  \w   -102.00 -69.00   1.00   10.00    --  -41.11 -38.00 -60.00   33
  7  \w    -39.00 -14.00   1.00   10.00    --  -41.11 -57.00  30.00   25
  8  \w    -86.00 -14.00   1.00   10.00    --  -41.11 -57.00-120.00   72
  9  \w     18.00  82.00   1.00   10.00    --   41.11  57.00 -60.00   64
 10  \w    153.00 178.00   1.00   12.00    --  107.58  77.00 -60.00   25
 11  \w    124.00 166.00   1.00   12.00    --  107.58  77.00-150.00   42
 12  \w     75.00 101.00   1.00   12.00    --  107.58  77.00 -30.00   26
 13  \w     78.00 104.00   1.00   12.00    --  107.58  61.00 -60.00   26
 14  \w     78.00 104.00   1.00   12.00    --  107.58  61.00-120.00   26
 15  \w     76.00 101.00   1.00   12.00    --  107.58  77.00-150.00   25
 16  \w     75.00 101.00   1.00   12.00    --  107.58  77.00 -60.00   26
 17  \w     82.00 109.00   1.00   12.00    --  107.58  45.00-120.00   27
 18  \w    119.00 161.00   1.00   12.00    --  107.58 125.00 -90.00   42
 19  \w     82.00 177.00   1.00   12.00    --  107.58  45.00 -60.00   95
 20  \w    148.00 175.00   1.00   12.00    --  107.58  77.00-120.00   27
 21  \w     79.00 104.00   1.00   12.00    --  107.58  61.00-150.00   25
 22  \w     83.00 112.00   1.00   12.00    --  107.58  45.00 -90.00   29
 23  \w     75.00 101.00   1.00   12.00    --  107.58  77.00 -90.00   26
 24  \w     83.00 108.00   1.00   12.00    --  107.58  45.00 -30.00   25
 25  \w     78.00 104.00   1.00   12.00    --  107.58  61.00 -90.00   26
 26  \w     33.00 113.00   1.00   12.00    --  107.58-116.00-134.00   80
 27  \w     78.00 104.00   1.00   12.00    --  107.58  61.00 -30.00   26
 28  \w     85.00 177.00   1.00   12.00    --  107.58  30.00 -90.00   92
 29  \w     84.00 125.00   1.00   12.00    --  107.58  30.00 -60.00   41
 30  \w     75.00 101.00   1.00   12.00    --  107.58  77.00-120.00   26
 31  \w     25.00  97.00   1.00   12.00    --  107.58 -94.00 120.00   72
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1150
_diffrn_reflns_av_unetI/netI     0.1617
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            56884
_diffrn_reflns_point_group_measured_fraction_full 0.944
_diffrn_reflns_point_group_measured_fraction_max 0.912
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.188
_diffrn_reflns_theta_min         3.449
_exptl_absorpt_coefficient_mu    0.584
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65525
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light colourless'
_exptl_crystal_density_diffrn    1.043
_exptl_crystal_description       block
_exptl_crystal_F_000             2640
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.430
_refine_diff_density_min         -0.293
_refine_diff_density_rms         0.077
_refine_ls_abs_structure_details
;
 Flack x determined using 1193 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.8(4)
_refine_ls_extinction_coef       0.00172(10)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   0.818
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     548
_refine_ls_number_reflns         9885
_refine_ls_number_restraints     487
_refine_ls_restrained_S_all      0.809
_refine_ls_R_factor_all          0.1524
_refine_ls_R_factor_gt           0.0870
_refine_ls_shift/su_max          0.008
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1249P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2086
_refine_ls_wR_factor_ref         0.2310
_reflns_Friedel_coverage         0.797
_reflns_Friedel_fraction_full    0.884
_reflns_Friedel_fraction_max     0.845
_reflns_number_gt                3893
_reflns_number_total             9885
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 117.3379\% 
 around [-0.05 0.03 1.00] (reciprocal) or [-0.01 0.00 1.00] (direct)

;
_cod_data_source_file            d3nj05076a2.cif
_cod_data_source_block           5
_cod_depositor_comments
'Adding full bibliography for 7062946--7062948.cif.'
_cod_original_cell_volume        7858.7(14)
_cod_database_code               7062948
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.944
_shelx_estimated_absorpt_t_min   0.928
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid body (RIGU) restrains
 C42, O5, C30, C33, C24, O6, H30, H33A, H33B, C34, C25, N4, C31, H34A, H34B,
 H34C, H25, C26, C28, H31A, H31B, C32, H26, C27, C29, H32A, H32B, H32C, H27,
 H29, N5, N6, O8, C35, C38, C39, C40, H35A, H35B, C36, C37, H38, O7, C41, C45,
 H36A, H36B, H37A, H37B, H41, C44, H45, H42, C43, C46, H43, H46A, H46B, H46C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.003
 N2, O1, C7, N1, C8, C6, C12, H8, C9, C5, C1, H12, C13, O2, C11, H9A, H9B, C10,
  C4, H5, H1, C2, C14, N3, H11A, H11B, H10A, H10B, C3, H4, C01N, H14, C15, C17,
 H3, H01A, H01B, H01C, H15, C16, C18, H16, O3, O4, H18, C19, C21, H19A, H19B,
 C20, H21A, H21B, C22, H20A, H20B, H20C, H22A, H22B, H22C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.003
 C34, O5, C30, C33, C24, O6, H30, H33A, H33B, C25, N4, C31, H34A, H34B, H34C,
 H25, C26, C28, H31A, H31B, C32, H26, C27, C29, H32A, H32B, H32C, H27, H29, N5,
 N6, O8, C35, C38, C39, C40, H35A, H35B, C36, C37, H38, O7, C41, C45, H36A,
 H36B, H37A, H37B, H41, C42, C44, H45, H42, C43, C46, H43, H46A, H46B, H46C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.004
 C3, O1, C7, N1, C8, C6, C12, H8, C9, N2, C5, C1, H12, C13, H9A, H9B, C10, O2,
 C11, C4, H5, H1, C2, C14, N3, H10A, H10B, H11A, H11B, H4, C01N, H14, C15, C17,
 H3, H01A, H01B, H01C, H15, C16, C18, H16, O3, O4, H18, C19, C21, H19A, H19B,
 C20, H21A, H21B, C22, H20A, H20B, H20C, H22A, H22B, H22C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.004
3.a Ternary CH refined with riding coordinates:
 C8(H8), C12(H12), C18(H18), C29(H29), C30(H30), C38(H38)
3.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C19(H19A,H19B), C21(H21A,H21B),
 C31(H31A,H31B), C33(H33A,H33B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B)
3.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C4(H4), C5(H5), C14(H14), C15(H15), C16(H16), C25(H25),
 C26(H26), C27(H27), C41(H41), C42(H42), C43(H43), C45(H45)
3.d Idealised Me refined as rotating group:
 C01N(H01A,H01B,H01C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C32(H32A,H32B,
 H32C), C34(H34A,H34B,H34C), C46(H46A,H46B,H46C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              21307
_shelx_fab_checksum              36551
_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
;