Stereodivergent assembly of δ-valerolactones with an azaarene-containing quaternary stereocenter enabled by Cu/Ru relay catalysis.
Tian, Kui; Jin, Zhuan; Liu, Xin-Lian; He, Ling; Liu, Hong-Fu; Yu, Pin-Ke; Chang, Xin; Dong, Xiu-Qin; Wang, Chun-Jiang; Chemical science 16 (2025) 1233–1240; doi:10.1039/d4sc05852f

data_1573402
_publ_section_title
;
 Stereodivergent assembly of &#x3b4;-valerolactones with an
 azaarene-containing quaternary stereocenter enabled by Cu/Ru relay
 catalysis.
;
_journal_issue                   3
_journal_name_full               'Chemical science'
_journal_page_first              1233
_journal_page_last               1240
_journal_paper_doi               10.1039/d4sc05852f
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C17 H16 F N O2'
_chemical_formula_sum            'C17 H16 F N O2'
_chemical_formula_weight         285.31
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2024-7-22
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2024-08-02 deposited with the CCDC.	2024-12-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.190(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.47670(10)
_cell_length_b                   15.7755(3)
_cell_length_c                   7.4250(2)
_cell_measurement_reflns_used    6257
_cell_measurement_temperature    300.20(10)
_cell_measurement_theta_max      73.0390
_cell_measurement_theta_min      5.5870
_cell_volume                     746.67(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.98a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.43.98a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.43.98a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      300.20(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.962
_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     26.00  74.00   0.50    0.20    --   64.58-125.00 -90.00   96
  2  \w     26.00  51.00   0.50    0.20    --   64.58-125.00 -60.00   50
  3  \w     26.00  52.00   0.50    0.20    --   64.58-125.00   0.00   52
  4  \w     28.00  75.00   0.50    0.20    --   64.58-125.00  60.00   94
  5  \w     32.00  63.00   0.50    0.20    --   69.43-125.00  90.00   62
  6  \w     36.00  61.00   0.50    0.20    --   69.43-125.00  60.00   50
  7  \w     65.00 108.00   0.50    0.20    --   69.43  15.00-150.00   86
  8  \w     77.00 102.00   0.50    0.20    --   64.58  15.00-120.00   50
  9  \w     71.00  97.00   0.50    0.20    --   64.58  15.00 -90.00   52
 10  \w     58.00  97.00   0.50    0.20    --   64.58  15.00  90.00   78
 11  \w   -102.00 -38.00   0.50    0.20    --  -76.00 140.00 -78.17  128
 12  \w   -104.00 -70.00   0.50    0.20    --  -77.72 139.00-103.07   68
 13  \w    -97.00 -71.00   0.50    0.20    --  -77.72 128.00 -37.54   52
 14  \w    -90.00 -36.00   0.50    0.20    --  -72.91 125.00-120.00  108
 15  \w    -81.00 -38.00   0.50    0.20    --  -72.91 125.00 -30.00   86
 16  \w    -55.00 -28.00   0.50    0.20    --  -66.36 125.00 -90.00   54
 17  \w    -57.00 -31.00   0.50    0.20    --  -66.36 125.00   0.00   52
 18  \w    -89.00 -34.00   0.50    0.20    --  -72.91 125.00  30.00  110
 19  \w    -55.00 -29.00   0.50    0.20    --  -66.36 125.00 150.00   52
 20  \w    -79.00 -54.00   0.50    0.20    --  -78.57 125.00 150.00   50
 21  \w    -72.00 -39.00   0.50    0.20    --  -72.91 125.00 120.00   66
 22  \w    -94.00 -69.00   0.50    0.20    --  -78.57 125.00  30.00   50
 23  \w    -95.00 -69.00   0.50    0.20    --  -78.57 125.00   0.00   52
 24  \w    -59.00 -29.00   0.50    0.20    --  -66.36 125.00-150.00   60
 25  \w    -95.00 -66.00   0.50    0.20    --  -78.57 125.00-120.00   58
 26  \w    -95.00 -69.00   0.50    0.20    --  -52.00 -22.00 -71.63   52
 27  \w    -92.00 -67.00   0.50    0.20    --  -52.00 -20.00 -61.07   50
 28  \w   -108.00 -83.00   0.50    0.20    --  -66.36 -15.00-120.00   50
 29  \w   -113.00 -70.00   0.50    0.20    --  -72.91 -15.00-150.00   86
 30  \w   -105.00 -77.00   0.50    0.20    --  -68.00 -18.00 -64.20   56
 31  \w   -113.00 -88.00   0.50    0.20    --  -72.91 -15.00 -90.00   50
 32  \w   -102.00 -77.00   0.50    0.20    --  -72.91 -15.00-120.00   50
 33  \w   -102.00 -66.00   0.50    0.20    --  -66.36 -15.00 -30.00   72
 34  \w   -107.00 -67.00   0.50    0.20    --  -72.91 -15.00   0.00   80
 35  \w   -120.00 -95.00   0.50    0.20    --  -78.57 -15.00 -60.00   50
 36  \w   -116.00 -85.00   0.50    0.20    --  -78.57 -15.00 -30.00   62
 37  \w   -107.00 -61.00   0.50    0.20    --  -66.36 -15.00  60.00   92
 38  \w   -107.00 -79.00   0.50    0.20    --  -78.57 -15.00  90.00   56
 39  \w   -113.00 -76.00   0.50    0.20    --  -72.91 -15.00 120.00   74
 40  \w   -104.00 -71.00   0.50    0.20    --  -66.36 -15.00 150.00   66
 41  \w   -102.00 -77.00   0.50    0.20    --  -78.57 -15.00 120.00   50
 42  \w   -105.00 -80.00   0.50    0.20    --  -78.57 -15.00  30.00   50
 43  \w   -119.00 -77.00   0.50    0.20    --  -78.57 -15.00-180.00   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0092512000
_diffrn_orient_matrix_UB_12      -0.0878539000
_diffrn_orient_matrix_UB_13      0.0915732000
_diffrn_orient_matrix_UB_21      0.2393903000
_diffrn_orient_matrix_UB_22      0.0089662000
_diffrn_orient_matrix_UB_23      0.0582142000
_diffrn_orient_matrix_UB_31      -0.0319451000
_diffrn_orient_matrix_UB_32      0.0416562000
_diffrn_orient_matrix_UB_33      0.1807492000
_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  0.0144
_diffrn_reflns_av_unetI/netI     0.0125
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            9329
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.927
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.689
_diffrn_reflns_theta_min         5.609
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.755
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79138
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.98a (Rigaku Oxford Diffraction, 2023)
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    1.269
_exptl_crystal_description       block
_exptl_crystal_F_000             300
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.163
_refine_diff_density_min         -0.141
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 1191 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(6)
_refine_ls_extinction_coef       0.0104(18)
_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   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     192
_refine_ls_number_reflns         2845
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0350
_refine_ls_R_factor_gt           0.0336
_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^)+(0.0590P)^2^+0.0244P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0930
_refine_ls_wR_factor_ref         0.0945
_reflns_Friedel_coverage         0.856
_reflns_Friedel_fraction_full    0.974
_reflns_Friedel_fraction_max     0.889
_reflns_number_gt                2694
_reflns_number_total             2845
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05852f2.cif
_cod_data_source_block           TK-lactone
_cod_depositor_comments          'Adding full bibliography for 1573402.cif.'
_cod_database_code               1573402
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N F'
_shelx_estimated_absorpt_t_max   0.805
_shelx_estimated_absorpt_t_min   0.660
_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.a Ternary CH refined with riding coordinates:
 C00E(H00E)
2.b Secondary CH2 refined with riding coordinates:
 C00A(H00A,H00B), C00H(H00H,H00I)
2.c Aromatic/amide H refined with riding coordinates:
 C009(H009), C00C(H00C), C00D(H00D), C00F(H00F), C00G(H00G), C00I(H00J),
 C00J(H00K), C00L(H00O)
2.d Idealised Me refined as rotating group:
 C00K(H00L,H00M,H00N)
;
_shelx_res_checksum              29045
_shelx_hkl_checksum              24888
_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 1.422
_oxdiff_exptl_absorpt_empirical_full_min 0.720