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_7132461
_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         'C21 H18 O6'
_chemical_formula_sum            'C21 H18 O6'
_chemical_formula_weight         366.35
_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   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-07-20
_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                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   7.60702(16)
_cell_length_b                   8.8987(2)
_cell_length_c                   25.6270(6)
_cell_measurement_reflns_used    3623
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      69.7440
_cell_measurement_theta_min      4.8740
_cell_volume                     1734.76(7)
_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 0.962
_diffrn_measured_fraction_theta_max 0.962
_diffrn_measurement_details
;
  1 omega  -28.00   10.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.5000  111.0000  150.0000 38

  2 omega  -86.00  -44.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.5000  178.0000  -90.0000 42

  3 omega  -66.00  -34.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.5000  178.0000   60.0000 32

  4 omega   64.00   90.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000 -125.0000 -180.0000 26

  5 omega   66.00  123.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   57.0000    0.0000 57

  6 omega   33.00   60.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   57.0000    0.0000 27

  7 omega   41.00  108.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000   60.0000 67

  8 omega   58.00   90.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000   60.0000 32

  9 omega   51.00   98.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -50.0000   30.0000 47

 10 omega   51.00   77.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000  150.0000 26

 11 omega   73.00  128.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  178.0000  -30.0000 55

 12 omega   79.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -50.0000  -30.0000 25

 13 omega   43.00   95.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -50.0000  120.0000 52

 14 omega   60.00   85.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  120.0000 25

 15 omega  -77.00  -47.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.5000  -57.0000   90.0000 30

 16 omega   50.00   85.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   57.0000   90.0000 35

 17 omega   63.00   93.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000  -60.0000 30

 18 omega  141.00  167.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000  150.0000 26

 19 omega  139.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   50.0000  -30.0000 39

 20 omega   86.00  119.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000  150.0000 33

 21 omega   59.00   90.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000  -90.0000 31

 22 omega   52.00   78.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000 -150.0000 26

 23 omega   35.00   68.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -25.0000    0.0000 33
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1271762000
_diffrn_orient_matrix_UB_12      0.1195772000
_diffrn_orient_matrix_UB_13      0.0214584000
_diffrn_orient_matrix_UB_21      -0.1454658000
_diffrn_orient_matrix_UB_22      -0.1198953000
_diffrn_orient_matrix_UB_23      0.0044736000
_diffrn_orient_matrix_UB_31      0.0603745000
_diffrn_orient_matrix_UB_32      -0.0362855000
_diffrn_orient_matrix_UB_33      0.0559822000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0198
_diffrn_reflns_av_unetI/netI     0.0266
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            5783
_diffrn_reflns_theta_full        66.59
_diffrn_reflns_theta_max         66.59
_diffrn_reflns_theta_min         5.26
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.859
_exptl_absorpt_correction_T_max  0.942
_exptl_absorpt_correction_T_min  0.893
_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             768
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.182
_refine_diff_density_min         -0.151
_refine_diff_density_rms         0.031
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.04(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     245
_refine_ls_number_reflns         2905
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0328
_refine_ls_R_factor_gt           0.0311
_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^)+(0.0471P)^2^+0.1770P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0812
_refine_ls_wR_factor_ref         0.0826
_reflns_number_gt                2763
_reflns_number_total             2905
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            d3cc05312a2.cif
_cod_data_source_block           12a
_cod_depositor_comments
'Adding full bibliography for 7132459--7132461.cif.'
_cod_original_cell_volume        1734.75(7)
_cod_database_code               7132461
_reflns_odcompleteness_completeness 95.96
_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:
 C10(H10), C11(H11), C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C13(H13A,H13B), C18(H18A,H18B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C15(H15), C16(H16)
2.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C)
;
_olex2_date_sample_data_collection 2018-07-20
_olex2_submission_special_instructions 'No special instructions were received'