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_1573300
_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 unk
_chemical_formula_moiety         'C30 H25 N O3'
_chemical_formula_sum            'C30 H25 N O3'
_chemical_formula_weight         447.51
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-03-27
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.09.11 svn.r3730fd0d for OlexSys, GUI svn.r6159)
;
_audit_update_record
;
2021-11-08 deposited with the CCDC.	2024-11-25 downloaded from the CCDC.
;
_cell_angle_alpha                93.702(2)
_cell_angle_beta                 109.012(2)
_cell_angle_gamma                103.102(2)
_cell_formula_units_Z            2
_cell_length_a                   9.9067(2)
_cell_length_b                   11.5214(3)
_cell_length_c                   11.6032(3)
_cell_measurement_reflns_used    6463
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      73.6480
_cell_measurement_theta_min      3.9630
_cell_volume                     1205.68(5)
_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 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (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      149.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.961
_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    -65.00  33.00   1.00    1.00    --  -40.73  38.00 -90.00   98
  2  \w      2.00  27.00   1.00    1.00    --   40.73 -99.00   0.00   25
  3  \w     47.00  93.00   1.00    1.00    --   40.73-125.00 -60.00   46
  4  \w     59.00  96.00   1.00    1.00    --   40.73-125.00  60.00   37
  5  \w     41.00  98.00   1.00    1.00    --  107.58-125.00  30.00   57
  6  \w     66.00 121.00   1.00    1.00    --  107.58-125.00  90.00   55
  7  \w     49.00  75.00   1.00    1.00    --  107.58-125.00 -60.00   26
  8  \w     87.00 117.00   1.00    1.00    --  107.58-125.00 -60.00   30
  9  \w     35.00 137.00   1.00    1.00    --  107.58 -61.00-180.00  102
 10  \w     57.00 174.00   1.00    1.00    --  107.58  15.00 -90.00  117
 11  \w    152.00 178.00   1.00    1.00    --  107.58 125.00-150.00   26
 12  \w     91.00 178.00   1.00    1.00    --  107.58  77.00 -60.00   87
 13  \w     84.00 125.00   1.00    1.00    --  107.58  77.00   0.00   41
 14  \w    119.00 178.00   1.00    1.00    --  107.58  61.00 150.00   59
 15  \w     35.00 130.00   1.00    1.00    --  107.58 -45.00   0.00   95
 16  \w     38.00  99.00   1.00    1.00    --  107.58 -94.00 150.00   61
 17  \w    -69.00  27.00   1.00    1.00    --  -40.73  57.00  30.00   96
 18  \w   -104.00 -18.00   1.00    1.00    --  -40.73 -38.00  90.00   86
;
_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      0.0799044000
_diffrn_orient_matrix_UB_12      -0.0961392000
_diffrn_orient_matrix_UB_13      0.0502100000
_diffrn_orient_matrix_UB_21      -0.1187125000
_diffrn_orient_matrix_UB_22      -0.0487667000
_diffrn_orient_matrix_UB_23      0.0562769000
_diffrn_orient_matrix_UB_31      -0.0926236000
_diffrn_orient_matrix_UB_32      -0.0875361000
_diffrn_orient_matrix_UB_33      -0.1203681000
_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  0.0204
_diffrn_reflns_av_unetI/netI     0.0266
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            8318
_diffrn_reflns_point_group_measured_fraction_full 0.607
_diffrn_reflns_point_group_measured_fraction_max 0.580
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.845
_diffrn_reflns_theta_min         3.985
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.630
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86440
_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            colorless
_exptl_crystal_density_diffrn    1.233
_exptl_crystal_description       block
_exptl_crystal_F_000             472
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.545
_refine_diff_density_min         -0.681
_refine_diff_density_rms         0.048
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.0(2)
_refine_ls_extinction_coef       0.0068(7)
_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   1.040
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     644
_refine_ls_number_reflns         5676
_refine_ls_number_restraints     50
_refine_ls_restrained_S_all      1.150
_refine_ls_R_factor_all          0.0403
_refine_ls_R_factor_gt           0.0392
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0616P)^2^+0.2642P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1031
_refine_ls_wR_factor_ref         0.1045
_reflns_Friedel_coverage         0.207
_reflns_Friedel_fraction_full    0.216
_reflns_Friedel_fraction_max     0.199
_reflns_number_gt                5503
_reflns_number_total             5676
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc06849a2.cif
_cod_data_source_block           exp_2926
_cod_depositor_comments
'Adding full bibliography for 1573300--1573302.cif.'
_cod_database_code               1573300
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 1.0(3)
 -0.0(3)
2. 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
3. Restrained distances
 C62-C61 = C60-C59
 1.32 with sigma of 0.01
 C62-C61 \\sim C60-C59
 with sigma of 0.02
4. Rigid bond restraints
 C61, C62
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C62, C61
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C59, C60
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Uiso/Uaniso restraints and constraints
C59 \\sim C60: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004 within 2A
C62 \\sim C61: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004 within 2A
Uanis(C59) \\sim Ueq, Uanis(C62) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
6. Rigid body (RIGU) restrains
 C58, C59, C60
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C58, C61, C62
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
7. Others
 Sof(H58A)=Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(C62)=1-FVAR(1)
 Sof(H58)=Sof(C59)=Sof(C60)=Sof(H60A)=Sof(H60B)=FVAR(1)
8.a Ternary CH refined with riding coordinates:
 C13(H13), C43(H43)
8.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C28(H28A,H28B), C44(H44A,H44B), C50(H50A,H50B)
8.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12),
 C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C24(H24), C32(H32), C33(H33),
  C34(H34), C35(H35), C36(H36), C38(H38), C39(H39), C41(H41), C42(H42),
 C53(H53), C54(H54), C55(H55), C56(H56), C57(H57), C58(H58A), C58(H58)
8.d X=CH2 refined with riding coordinates:
 C60(H60A,H60B), C61(H61A,H61B)
8.e Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C51(H51A,H51B,H51C)
;
_shelx_res_checksum              62300
_shelx_hkl_checksum              2945
_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 1.361
_oxdiff_exptl_absorpt_empirical_full_min 0.507