Intramolecular Ni-catalyzed reductive coupling enables enantiodivergent synthesis of linoxepin.
Liu, Zi-Hao; Xiao, Jian; Zhai, Qian-Qian; Tang, Xi; Xu, Li-Jun; Zhuang, Zhi-Yuan; Wang, Ya-Wen; Peng, Yu; Chemical communications (Cambridge, England) 60 (2024) 694–697; doi:10.1039/d3cc05312a

data_7132460
_publ_section_title
;
 Intramolecular Ni-catalyzed reductive coupling enables enantiodivergent
 synthesis of linoxepin.
;
_journal_issue                   6
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              694
_journal_page_last               697
_journal_paper_doi               10.1039/d3cc05312a
_journal_volume                  60
_journal_year                    2024
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C22 H22 O6'
_chemical_formula_sum            'C22 H22 O6'
_chemical_formula_weight         382.39
_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             2022-06-09
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2023-10-05 deposited with the CCDC.	2023-12-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.41567(15)
_cell_length_b                   11.8302(3)
_cell_length_c                   18.4063(3)
_cell_measurement_reflns_used    5342
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      77.0250
_cell_measurement_theta_min      4.4200
_cell_volume                     1832.51(6)
_computing_cell_refinement       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.946
_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     35.00  60.00   0.50    0.10    --  107.75 -57.00  60.00   50
  2  \w     36.00  61.00   0.50    0.10    --  107.75 -57.00  30.00   50
  3  \w    -16.00  22.00   0.50    0.05    --   47.57 -19.00-120.00   76
  4  \w    -27.00  -2.00   0.50    0.05    --   47.57 -19.00   0.00   50
  5  \w     35.00  60.00   0.50    0.10    --  107.75 -57.00 -60.00   50
  6  \w     38.00  63.00   0.50    0.10    --  107.75 -57.00 -90.00   50
  7  \w     36.00  61.00   0.50    0.10    --  107.75 -57.00-120.00   50
  8  \w     41.00  67.00   0.50    0.10    --  107.75 -99.00 -60.00   52
  9  \w     76.00 106.00   0.50    0.10    --  107.75 -99.00 -60.00   60
 10  \w    -75.00 -23.00   0.50    0.05    --  -47.57  99.00 102.00  104
 11  \w    -27.00  24.00   0.50    0.05    --  -47.57  19.00 -30.00  102
 12  \w    -57.00 -31.00   0.50    0.10    -- -100.00  57.00   0.00   52
 13  \w   -170.00-104.00   0.50    0.10    -- -100.00 -39.00  99.00  132
 14  \w   -144.00-102.00   0.50    0.10    -- -100.00 -99.00  -3.00   84
 15  \w   -169.00 -91.00   0.50    0.10    -- -100.00 -94.00-103.00  156
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1136794000
_diffrn_orient_matrix_UB_12      0.0800414000
_diffrn_orient_matrix_UB_13      0.0407861000
_diffrn_orient_matrix_UB_21      -0.1264535000
_diffrn_orient_matrix_UB_22      0.0942346000
_diffrn_orient_matrix_UB_23      -0.0025038000
_diffrn_orient_matrix_UB_31      -0.0679530000
_diffrn_orient_matrix_UB_32      -0.0414080000
_diffrn_orient_matrix_UB_33      0.0728897000
_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  0.0362
_diffrn_reflns_av_unetI/netI     0.0440
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.946
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            7110
_diffrn_reflns_point_group_measured_fraction_full 0.924
_diffrn_reflns_point_group_measured_fraction_max 0.852
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.392
_diffrn_reflns_theta_min         4.443
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.833
_exptl_absorpt_correction_T_max  0.967
_exptl_absorpt_correction_T_min  0.890
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.113a (Rigaku Oxford Diffraction, 2021)
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    1.386
_exptl_crystal_description       block
_exptl_crystal_F_000             808
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.223
_refine_diff_density_min         -0.170
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 1089 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.06(12)
_refine_ls_extinction_coef       0.0016(3)
_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   1.069
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     264
_refine_ls_number_reflns         3323
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0370
_refine_ls_R_factor_gt           0.0339
_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^)+(0.0409P)^2^+0.1626P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0850
_refine_ls_wR_factor_ref         0.0870
_reflns_Friedel_coverage         0.572
_reflns_Friedel_fraction_full    0.824
_reflns_Friedel_fraction_max     0.726
_reflns_number_gt                3113
_reflns_number_total             3323
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc05312a2.cif
_cod_data_source_block           11b
_cod_depositor_comments
'Adding full bibliography for 7132459--7132461.cif.'
_cod_original_cell_volume        1832.52(6)
_cod_database_code               7132460
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.967
_shelx_estimated_absorpt_t_min   0.892
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C7(H7), C8(H8), C9(H9), C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C20(H20A,H20B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C14(H14), C15(H15)
2.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C22(H22A,H22B,H22C)
;
_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 2.709
_oxdiff_exptl_absorpt_empirical_full_min 0.699