Enantioselective palladium-catalyzed carbonylation toward N-N axially chiral amides.
Li, Ke-Jiao; Geng, Ying-Ying; Zhang, Fu-Jian; Li, Xin-Yue; Liu, Jing-Wen; Wu, Cheng-Gui; Feng, Cheng-Tao; Teng, Fan; Organic & biomolecular chemistry 23 (2025) 9105–9109; doi:10.1039/d5ob01298h

data_7160751
_publ_section_title
;
 Enantioselective palladium-catalyzed carbonylation toward N-N axially
 chiral amides.
;
_journal_issue                   40
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              9105
_journal_page_last               9109
_journal_paper_doi               10.1039/d5ob01298h
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C17 H10 Cl N3 O3'
_chemical_formula_sum            'C17 H10 Cl N3 O3'
_chemical_formula_weight         339.73
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-01-12
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-04-28 deposited with the CCDC.	2025-09-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   47.8889(7)
_cell_length_b                   12.8413(2)
_cell_length_c                   9.75090(10)
_cell_measurement_reflns_used    43135
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      76.5860
_cell_measurement_theta_min      2.6980
_cell_volume                     5996.37(14)
_computing_cell_refinement       'CrysAlisPro 1.171.42.95a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.95a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.95a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.977
_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     19.00  92.05   0.15    0.03    --   47.13-125.00  90.00  487
  2  \w     38.00 111.05   0.15    0.03    --  107.18-125.00  30.00  487
  3  \w     38.00 107.00   0.15    0.03    --  107.18-106.00  16.00  460
  4  \w     37.00 106.00   0.15    0.03    --  107.18 -99.00 -60.00  460
  5  \w     35.00  68.00   0.15    0.03    --  107.18 -57.00  60.00  220
  6  \w     35.00 107.00   0.15    0.03    --  107.18 -77.00 120.00  480
  7  \w     35.00  68.00   0.15    0.03    --  107.18 -57.00  30.00  220
  8  \w     35.00  68.00   0.15    0.03    --  107.18 -57.00 -60.00  220
  9  \w     35.00 107.00   0.15    0.03    --  107.18 -77.00-180.00  480
 10  \w     35.00  68.00   0.15    0.03    --  107.18 -57.00-180.00  220
 11  \w     35.00  68.00   0.15    0.03    --  107.18 -57.00-150.00  220
 12  \w     35.00 109.10   0.15    0.03    --   47.13  38.00  30.00  494
 13  \w     25.00 119.05   0.15    0.03    --   47.13  77.00  60.00  627
 14  \w     25.00 119.05   0.15    0.03    --   47.13  77.00 120.00  627
 15  \w    -23.00  28.00   0.15    0.03    --  -47.13  19.00 -60.00  340
 16  \w    -63.00 -30.00   0.15    0.03    -- -103.00  57.00 -60.00  220
 17  \w    -63.00 -30.00   0.15    0.03    -- -103.00  57.00-150.00  220
 18  \w    -23.00  28.00   0.15    0.03    --  -47.13  19.00-150.00  340
 19  \w   -122.00 -35.00   0.15    0.03    --  -47.13 -21.00-175.00  580
 20  \w   -174.00 -90.00   0.15    0.03    -- -103.00 -21.00-175.00  560
 21  \w   -119.00 -32.00   0.15    0.03    --  -47.13 -57.00 -60.00  580
 22  \w   -112.00 -34.00   0.15    0.03    -- -103.00 125.00  60.00  520
 23  \w   -109.00 -34.00   0.15    0.03    -- -103.00 123.00-162.00  500
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0124630000
_diffrn_orient_matrix_UB_12      0.1106158000
_diffrn_orient_matrix_UB_13      -0.0021359000
_diffrn_orient_matrix_UB_21      0.0285196000
_diffrn_orient_matrix_UB_22      -0.0449844000
_diffrn_orient_matrix_UB_23      -0.0434637000
_diffrn_orient_matrix_UB_31      -0.0082079000
_diffrn_orient_matrix_UB_32      0.0113879000
_diffrn_orient_matrix_UB_33      -0.1518132000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0715
_diffrn_reflns_av_unetI/netI     0.0372
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       59
_diffrn_reflns_limit_h_min       -59
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            55945
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.605
_diffrn_reflns_theta_min         1.845
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.456
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56439
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.95a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.505
_exptl_crystal_description       block
_exptl_crystal_F_000             2784
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.476
_refine_diff_density_min         -0.377
_refine_diff_density_rms         0.072
_refine_ls_abs_structure_details
;
 Flack x determined using 4575 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.024(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.102
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1069
_refine_ls_number_reflns         12269
_refine_ls_number_restraints     794
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0605
_refine_ls_R_factor_gt           0.0588
_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^)+(0.0225P)^2^+15.2303P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1310
_refine_ls_wR_factor_ref         0.1318
_reflns_Friedel_coverage         0.759
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.937
_reflns_number_gt                11829
_reflns_number_total             12269
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01298h2.cif
_cod_data_source_block           tf_auto
_cod_depositor_comments          'Adding full bibliography for 7160751.cif.'
_cod_database_code               7160751
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHONCl
_shelx_estimated_absorpt_t_max   0.828
_shelx_estimated_absorpt_t_min   0.791
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl2-C19 \\sim Cl2A-C19A
 with sigma of 0.02
 O4-C24 \\sim O4A-C24A
 with sigma of 0.02
 O5-C25 \\sim O5A-C25A
 with sigma of 0.02
 N4-C24 \\sim N4-C24A
 with sigma of 0.02
 N4-C25 \\sim N4-C25A
 with sigma of 0.02
 C23-C24 \\sim C23A-C24A
 with sigma of 0.02
 C23-C22 \\sim C23A-C22A
 with sigma of 0.02
 C23-C18 \\sim C23A-C18A
 with sigma of 0.02
 C22-C25 \\sim C22A-C25A
 with sigma of 0.02
 C22-C21 \\sim C22A-C21A
 with sigma of 0.02
 C18-C19 \\sim C18A-C19A
 with sigma of 0.02
 C20-C19 \\sim C20A-C19A
 with sigma of 0.02
 C20-C21 \\sim C20A-C21A
 with sigma of 0.02
 Cl2-C18 \\sim Cl2A-C18A
 with sigma of 0.04
 Cl2-C20 \\sim Cl2A-C20A
 with sigma of 0.04
 O4-N4 \\sim O4A-N4
 with sigma of 0.04
 O4-C23 \\sim O4A-C23A
 with sigma of 0.04
 O5-N4 \\sim O5A-N4
 with sigma of 0.04
 O5-C22 \\sim O5A-C22A
 with sigma of 0.04
 N4-C23 \\sim N4-C23A
 with sigma of 0.04
 N4-C22 \\sim N4-C22A
 with sigma of 0.04
 C23-C25 \\sim C23A-C25A
 with sigma of 0.04
 C23-C19 \\sim C23A-C19A
 with sigma of 0.04
 C23-C21 \\sim C23A-C21A
 with sigma of 0.04
 C24-C22 \\sim C24A-C22A
 with sigma of 0.04
 C24-C18 \\sim C24A-C18A
 with sigma of 0.04
 C22-C18 \\sim C22A-C18A
 with sigma of 0.04
 C22-C20 \\sim C22A-C20A
 with sigma of 0.04
 C18-C20 \\sim C18A-C20A
 with sigma of 0.04
 C25-C21 \\sim C25A-C21A
 with sigma of 0.04
 C19-C21 \\sim C19A-C21A
 with sigma of 0.04
 Cl4-C54 \\sim Cl4A-C54A
 with sigma of 0.02
 O10-C58 \\sim O10A-C58A
 with sigma of 0.02
 O11-C59 \\sim O11A-C59A
 with sigma of 0.02
 N10-C58 \\sim N10-C58A
 with sigma of 0.02
 N10-C59 \\sim N10-C59A
 with sigma of 0.02
 C57-C58 \\sim C57A-C58A
 with sigma of 0.02
 C57-C56 \\sim C57A-C56A
 with sigma of 0.02
 C57-C52 \\sim C57A-C52A
 with sigma of 0.02
 C56-C55 \\sim C56A-C55A
 with sigma of 0.02
 C56-C59 \\sim C56A-C59A
 with sigma of 0.02
 C52-C53 \\sim C52A-C53A
 with sigma of 0.02
 C55-C54 \\sim C55A-C54A
 with sigma of 0.02
 C53-C54 \\sim C53A-C54A
 with sigma of 0.02
 Cl4-C55 \\sim Cl4A-C55A
 with sigma of 0.04
 Cl4-C53 \\sim Cl4A-C53A
 with sigma of 0.04
 O10-N10 \\sim O10A-N10
 with sigma of 0.04
 O10-C57 \\sim O10A-C57A
 with sigma of 0.04
 O11-N10 \\sim O11A-N10
 with sigma of 0.04
 O11-C56 \\sim O11A-C56A
 with sigma of 0.04
 N10-C57 \\sim N10-C57A
 with sigma of 0.04
 N10-C56 \\sim N10-C56A
 with sigma of 0.04
 C57-C55 \\sim C57A-C55A
 with sigma of 0.04
 C57-C59 \\sim C57A-C59A
 with sigma of 0.04
 C57-C53 \\sim C57A-C53A
 with sigma of 0.04
 C58-C56 \\sim C58A-C56A
 with sigma of 0.04
 C58-C52 \\sim C58A-C52A
 with sigma of 0.04
 C56-C52 \\sim C56A-C52A
 with sigma of 0.04
 C56-C54 \\sim C56A-C54A
 with sigma of 0.04
 C52-C54 \\sim C52A-C54A
 with sigma of 0.04
 C55-C59 \\sim C55A-C59A
 with sigma of 0.04
 C55-C53 \\sim C55A-C53A
 with sigma of 0.04
3. Restrained planarity
 Cl2A, O4A, O5A, N4, C18A, H18A, C19A, C20A, H20A, C21A, H21A, C22A, C23A,
 C24A, C25A
 with sigma of 0.1
 Cl4A, O10A, O11A, N10, C52A, H52A, C53A, H53A, C54A, C55A, H55A, C56A, C57A,
 C58A, C59A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Cl4 \\sim C53 \\sim C54 \\sim C55: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
Cl2 \\sim Cl2A \\sim O4 \\sim O4A \\sim O5 \\sim O5A \\sim N4 \\sim N5 \\sim
C18 \\sim C18A \\sim C19 \\sim C19A \\sim C20 \\sim C20A \\sim C21 \\sim C21A
\\sim C22 \\sim C22A \\sim C23 \\sim C23A \\sim C24 \\sim C24A \\sim C25 \\sim
C25A: within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002
within 2A
Cl4 \\sim Cl4A \\sim O10 \\sim O10A \\sim O11 \\sim O11A \\sim N10 \\sim N11
\\sim C52 \\sim C52A \\sim C53 \\sim C53A \\sim C54 \\sim C54A \\sim C55 \\sim
C55A \\sim C56 \\sim C56A \\sim C57 \\sim C57A \\sim C58 \\sim C58A \\sim C59
\\sim C59A: within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002
within 2A
5. Others
 Sof(Cl2A)=Sof(O4A)=Sof(O5A)=Sof(C18A)=Sof(H18A)=Sof(C19A)=Sof(C20A)=Sof(H20A)=
 Sof(C21A)=Sof(H21A)=Sof(C22A)=Sof(C23A)=Sof(C24A)=Sof(C25A)=1-FVAR(1)
 Sof(Cl2)=Sof(O4)=Sof(O5)=Sof(C18)=Sof(H18)=Sof(C19)=Sof(C20)=Sof(H20)=
 Sof(C21)=Sof(H21)=Sof(C22)=Sof(C23)=Sof(C24)=Sof(C25)=FVAR(1)
 Sof(Cl4A)=Sof(O10A)=Sof(O11A)=Sof(C52A)=Sof(H52A)=Sof(C53A)=Sof(H53A)=
 Sof(C54A)=Sof(C55A)=Sof(H55A)=Sof(C56A)=Sof(C57A)=Sof(C58A)=Sof(C59A)=1-FVAR(2)
 Sof(Cl4)=Sof(O10)=Sof(O11)=Sof(C52)=Sof(H52)=Sof(C53)=Sof(H53)=Sof(C54)=
 Sof(C55)=Sof(H55)=Sof(C56)=Sof(C57)=Sof(C58)=Sof(C59)=FVAR(2)
6.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C14(H14), C15(H15), C17(H17), C18(H18),
 C18A(H18A), C20(H20), C20A(H20A), C21(H21), C21A(H21A), C28(H28), C29(H29),
 C30(H30), C31(H31), C35(H35), C36(H36), C37(H37), C38(H38), C47(H47), C48(H48),
  C50(H50), C52(H52), C52A(H52A), C53(H53), C53A(H53A), C55(H55), C55A(H55A),
 C62(H62), C63(H63), C64(H64), C65(H65)
6.b Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C34(H34A,H34B,H34C), C43(H43A,H43B,H43C), C68(H68A,H68B,H68C)
;
_shelx_res_checksum              22529
_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 2.048
_oxdiff_exptl_absorpt_empirical_full_min 0.651