Cobalt-catalyzed enantioselective desymmetrizing reductive cyclization of alkynyl cyclodiketones.
Liang, Ren-Xiao; Tang, Heng-Wei; Liu, Jia-Liang; Xu, Jian-Feng; Chen, Ling-Jia; Jia, Yi-Xia; Chemical science 14 (2023) 6393–6398; doi:10.1039/d3sc00119a

data_1569185
_publ_section_title
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 Cobalt-catalyzed enantioselective desymmetrizing reductive cyclization of
 alkynyl cyclodiketones.
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_journal_issue                   23
_journal_name_full               'Chemical science'
_journal_page_first              6393
_journal_page_last               6398
_journal_paper_doi               10.1039/d3sc00119a
_journal_volume                  14
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H16 O2 S'
_chemical_formula_sum            'C18 H16 O2 S'
_chemical_formula_weight         296.37
_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     dual
_audit_creation_date             2020-07-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-07-08 deposited with the CCDC.	2023-05-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.349(2)
_cell_length_b                   11.275(3)
_cell_length_c                   17.533(4)
_cell_measurement_reflns_used    9911
_cell_measurement_temperature    170(2)
_cell_measurement_theta_max      27.09
_cell_measurement_theta_min      3.01
_cell_volume                     1452.8(6)
_computing_cell_refinement       SAINT
_computing.data_collection       Bruker
_computing.data_reduction        SAINT
_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_temperature      170.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'zju Bruker D8 Venture Ims3.0'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0278
_diffrn_reflns_av_unetI/netI     0.0219
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            17267
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.036
_diffrn_reflns_theta_min         2.323
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.224
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.7079
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0799 before and 0.0435 after correction.
The Ratio of minimum to maximum transmission is 0.9496.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.355
_exptl_crystal_description       block
_exptl_crystal_F_000             624
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.29
_refine_diff_density_max         0.229
_refine_diff_density_min         -0.253
_refine_diff_density_rms         0.061
_refine_ls_abs_structure_details
;
 Flack x determined using 1314 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     232
_refine_ls_number_reflns         3192
_refine_ls_number_restraints     132
_refine_ls_restrained_S_all      1.098
_refine_ls_R_factor_all          0.0285
_refine_ls_R_factor_gt           0.0280
_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^)+(0.0470P)^2^+0.1810P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0740
_refine_ls_wR_factor_ref         0.0748
_reflns_Friedel_coverage         0.726
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                3144
_reflns_number_total             3192
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc00119a2.cif
_cod_data_source_block           200730_thw_p22_0m
_cod_depositor_comments          'Adding full bibliography for 1569185.cif.'
_cod_database_code               1569185
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.938
_shelx_estimated_absorpt_t_min   0.900
_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. Uiso/Uaniso restraints and constraints
C5 \\sim S1 \\sim C1 \\sim C2 \\sim C3 \\sim C4 \\sim S1A \\sim C1A \\sim C2A
\\sim C3A \\sim C4A: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C3) = Uanis(C3A)
3. Others
 Sof(H5B)=Sof(S1A)=Sof(C1A)=Sof(H1AA)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=
 Sof(C4A)=1-FVAR(1)
 Sof(H5A)=Sof(S1)=Sof(C1)=Sof(H1A)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=
 FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C16(H16A,H16B)
4.b Aromatic/amide H refined with riding coordinates:
 C5(H5A), C5(H5B), C8(H8), C9(H9), C10(H10), C11(H11), C1(H1A), C2(H2), C3(H3),
  C1A(H1AA), C2A(H2A), C3A(H3A)
4.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C)
4.d Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              96695
_olex2_submission_special_instructions 'No special instructions were received'