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_7132459
_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 ad
_chemical_formula_moiety         'C32 H31 Br O6'
_chemical_formula_sum            'C32 H31 Br O6'
_chemical_formula_weight         591.48
_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-08-22
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_audit_update_record
;
2023-10-05 deposited with the CCDC.	2023-12-10 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 97.286(5)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   10.8450(5)
_cell_length_b                   11.7874(6)
_cell_length_c                   11.0385(5)
_cell_measurement_reflns_used    1481
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      22.4190
_cell_measurement_theta_min      3.9530
_cell_volume                     1399.71(12)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
  1 omega  -18.00   19.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.4273  -99.0000 -120.0000 37

  2 omega  -20.00    5.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.4273  -99.0000    0.0000 25

  3 omega  -46.00   65.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867  -19.0000 -180.0000 111

  4 omega   43.00  101.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867  178.0000 -120.0000 58
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0063172000
_diffrn_orient_matrix_UB_12      0.0546370000
_diffrn_orient_matrix_UB_13      0.0253888000
_diffrn_orient_matrix_UB_21      0.0218692000
_diffrn_orient_matrix_UB_22      0.0249664000
_diffrn_orient_matrix_UB_23      -0.0517234000
_diffrn_orient_matrix_UB_31      -0.0618886000
_diffrn_orient_matrix_UB_32      0.0032437000
_diffrn_orient_matrix_UB_33      -0.0296326000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0320
_diffrn_reflns_av_unetI/netI     0.0667
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            5394
_diffrn_reflns_theta_full        26.02
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         3.31
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.512
_exptl_absorpt_correction_T_max  0.773
_exptl_absorpt_correction_T_min  0.713
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
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    1.403
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             612
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.272
_refine_diff_density_min         -0.437
_refine_diff_density_rms         0.062
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.007(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     354
_refine_ls_number_reflns         3860
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.010
_refine_ls_R_factor_all          0.0614
_refine_ls_R_factor_gt           0.0432
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0296P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0773
_refine_ls_wR_factor_ref         0.0865
_reflns_number_gt                3105
_reflns_number_total             3860
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            d3cc05312a2.cif
_cod_data_source_block           3
_cod_depositor_comments
'Adding full bibliography for 7132459--7132461.cif.'
_cod_original_cell_volume        1399.71(11)
_cod_database_code               7132459
_reflns_odcompleteness_completeness 99.67
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C16(H16)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C23(H23A,H23B), C24(H24A,H24B),
 C26(H26A,H26B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4A), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C19(H19),
 C20(H20), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32)
2.d Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C)
2.e Idealised tetrahedral OH refined as rotating group:
 O4(H4)
;
_olex2_date_sample_data_collection 2018-08-21
_olex2_submission_special_instructions 'No special instructions were received'