Ni-catalyzed asymmetric decarboxylation for the construction of carbocycles with contiguous quaternary carbon stereocenters.
He, Yicheng; Yan, Biwei; Ma, Cheng; Ni, Shaofei; Guo, Wusheng; Chemical science 16 (2025) 834–839; doi:10.1039/d4sc06849a

data_1573302
_publ_section_title
;
 Ni-catalyzed asymmetric decarboxylation for the construction of
 carbocycles with contiguous quaternary carbon stereocenters.
;
_journal_issue                   2
_journal_name_full               'Chemical science'
_journal_page_first              834
_journal_page_last               839
_journal_paper_doi               10.1039/d4sc06849a
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C28 H21 N O2'
_chemical_formula_sum            'C28 H21 N O2'
_chemical_formula_weight         403.46
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-07-26
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2024-10-08 deposited with the CCDC.	2024-11-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.22984(13)
_cell_length_b                   15.4298(4)
_cell_length_c                   22.0803(5)
_cell_measurement_reflns_used    8462
_cell_measurement_temperature    170.00(10)
_cell_measurement_theta_max      73.5370
_cell_measurement_theta_min      2.7760
_cell_volume                     2122.47(9)
_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 2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      170.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.986
_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   -129.00  47.00   1.00    1.00    --  -40.73   0.00-150.00  176
  2  \w     23.00  97.00   1.00    1.00    --   40.73-125.00 -30.00   74
  3  \w      1.00  82.00   1.00    1.00    --   40.73 -99.00-150.00   81
  4  \w     34.00 121.00   1.00    1.00    --  106.95-125.00  60.00   87
  5  \w     34.00 121.00   1.00    1.00    --  106.95-125.00-180.00   87
  6  \w     94.00 178.00   1.00    1.00    --  106.95 125.00 120.00   84
  7  \w     81.00 178.00   1.00    1.00    --  106.95  45.00  60.00   97
  8  \w     79.00 178.00   1.00    1.00    --  106.95  30.00 -60.00   99
  9  \w     25.00 109.00   1.00    1.00    --  106.95 -95.00-150.00   84
 10  \w   -115.00 -16.00   1.00    1.00    --  -40.73 -38.00 120.00   99
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0279567000
_diffrn_orient_matrix_UB_12      0.0458681000
_diffrn_orient_matrix_UB_13      -0.0614769000
_diffrn_orient_matrix_UB_21      0.0689909000
_diffrn_orient_matrix_UB_22      0.0863807000
_diffrn_orient_matrix_UB_23      0.0290413000
_diffrn_orient_matrix_UB_31      0.2359302000
_diffrn_orient_matrix_UB_32      -0.0197882000
_diffrn_orient_matrix_UB_33      -0.0157129000
_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  0.0305
_diffrn_reflns_av_unetI/netI     0.0314
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            11751
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.463
_diffrn_reflns_theta_min         3.495
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.624
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57701
_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    1.263
_exptl_crystal_description       block
_exptl_crystal_F_000             848
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.205
_refine_diff_density_min         -0.154
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 1562 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(12)
_refine_ls_extinction_coef       0.0058(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     289
_refine_ls_number_reflns         4186
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0357
_refine_ls_R_factor_gt           0.0337
_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^)+(0.0509P)^2^+0.1089P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0863
_refine_ls_wR_factor_ref         0.0879
_reflns_Friedel_coverage         0.714
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.966
_reflns_number_gt                4006
_reflns_number_total             4186
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc06849a2.cif
_cod_data_source_block           546-2
_cod_depositor_comments
'Adding full bibliography for 1573300--1573302.cif.'
_cod_original_cell_volume        2122.48(8)
_cod_database_code               1573302
_shelx_shelxl_version_number     2017/1
_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), C13(H13)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C15(H15), C16(H16), C18(H18),
 C19(H19), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26)
;
_shelx_res_checksum              48546
_shelx_hkl_checksum              33540
_olex2_date_sample_data_collection 2022-07-25
_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 2.113
_oxdiff_exptl_absorpt_empirical_full_min 0.464