Nickel-catalysed asymmetric hydromonofluoromethylation of 1,3-enynes for enantioselective construction of monofluoromethyl-tethered chiral allenes.
Zhang, Ying; Yang, Jimin; Ruan, Yu-Long; Liao, Ling; Ma, Chuang; Xue, Xiao-Song; Yu, Jin-Sheng; Chemical science 14 (2023) 12676–12683; doi:10.1039/d3sc04474b

data_1570176
_publ_section_title
;
 Nickel-catalysed asymmetric hydromonofluoromethylation of 1,3-enynes for
 enantioselective construction of monofluoromethyl-tethered chiral
 allenes.
;
_journal_issue                   44
_journal_name_full               'Chemical science'
_journal_page_first              12676
_journal_page_last               12683
_journal_paper_doi               10.1039/d3sc04474b
_journal_volume                  14
_journal_year                    2023
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C24 H20 F2 O4 S2'
_chemical_formula_sum            'C24 H20 F2 O4 S2'
_chemical_formula_weight         474.52
_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             2023-06-27
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-06-27 deposited with the CCDC.	2023-10-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.4390(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.1305(2)
_cell_length_b                   10.80990(10)
_cell_length_c                   23.0760(3)
_cell_measurement_reflns_used    16708
_cell_measurement_temperature    297.96(14)
_cell_measurement_theta_max      74.1870
_cell_measurement_theta_min      3.8710
_cell_volume                     2258.43(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (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      297.96(14)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -24.00  86.00   1.00    1.00    --    0.00  19.00 120.00  110
  2  \w     13.00  55.00   1.00    1.00    --    0.00  77.00 -30.00   42
  3  \w    -16.00  22.00   1.00    1.00    --    0.00  37.00 -90.00   38
  4  \w    -16.00  20.00   1.00    1.00    --    0.00  37.00-120.00   36
  5  \w    -56.00  18.00   1.00    1.00    --    0.00 -37.00 -30.00   74
  6  \w     58.00  88.00   1.00    1.00    --    0.00  37.00-120.00   30
  7  \w     31.00  87.00   1.00    1.00    --    0.00  37.00 -90.00   56
  8  \w    -82.00  18.00   1.00    1.00    --    0.00 -57.00 -60.00  100
  9  \w    -30.00  22.00   1.00    1.00    --    0.00  77.00 150.00   52
 10  \w     36.00  86.00   1.00    1.00    --    0.00  77.00 150.00   50
 11  \w    -30.00   0.00   1.00    1.00    --    0.00  77.00 -30.00   30
 12  \w     63.00  89.00   1.00    2.00    --   95.80  82.00-158.05   26
 13  \w     72.00  98.00   1.00    2.00    --   95.80  56.00 -34.72   26
 14  \w    150.00 176.00   1.00    2.00    --   95.80  82.00-158.05   26
 15  \w    160.00 185.00   1.00    2.00    --   95.80  72.00  53.06   25
 16  \w     67.00  92.00   1.00    2.00    --   95.80  72.00  53.06   25
 17  \w     74.00 185.00   1.00    2.00    --   95.80  53.00-122.78  111
 18  \w     75.00 109.00   1.00    2.00    --   95.80  43.00-161.33   34
 19  \w     63.00  89.00   1.00    2.00    --   95.80  82.00 120.00   26
 20  \w     65.00  91.00   1.00    2.00    --   95.80  76.00 -11.07   26
 21  \w     87.00 126.00   1.00    2.00    --   95.80 -82.00   0.00   39
 22  \w     66.00  92.00   1.00    2.00    --   95.80  77.00-120.00   26
 23  \w     63.00  89.00   1.00    2.00    --   95.80  82.00   0.00   26
 24  \w     72.00 184.00   1.00    2.00    --   95.80  61.00 150.00  112
 25  \w     63.00  88.00   1.00    2.00    --   95.80  82.00 -60.00   25
 26  \w     63.00  89.00   1.00    2.00    --   95.80  82.00 150.00   26
 27  \w     65.00  90.00   1.00    2.00    --   95.80  77.00 -30.00   25
 28  \w    114.00 140.00   1.00    2.00    --   95.80  77.00 -30.00   26
 29  \w     65.00  90.00   1.00    2.00    --   95.80  77.00  30.00   25
 30  \w     65.00  91.00   1.00    2.00    --   95.80  82.00-150.00   26
 31  \w     65.00  91.00   1.00    2.00    --   95.80  77.00-180.00   26
 32  \w    143.00 182.00   1.00    2.00    --   95.80  63.00  39.28   39
 33  \w     69.00 185.00   1.00    2.00    --   95.80  67.00 124.55  116
 34  \w     75.00 104.00   1.00    2.00    --   95.80  45.00 -90.00   29
 35  \w     65.00  91.00   1.00    2.00    --   95.80  77.00 -90.00   26
 36  \w     65.00  90.00   1.00    2.00    --   95.80  77.00 120.00   25
 37  \w    110.00 140.00   1.00    2.00    --   95.80  77.00  60.00   30
 38  \w    140.00 168.00   1.00    2.00    --   95.80  45.00 -90.00   28
 39  \w     71.00  97.00   1.00    2.00    --   95.80  61.00   0.00   26
 40  \w     65.00  91.00   1.00    2.00    --   95.80  77.00  90.00   26
 41  \w     70.00 126.00   1.00    2.00    --   95.80  63.00  39.28   56
 42  \w     63.00  88.00   1.00    2.00    --   95.80  82.00  60.00   25
 43  \w     65.00 104.00   1.00    2.00    --   95.80  77.00  60.00   39
 44  \w     71.00  96.00   1.00    2.00    --   95.80  61.00 -30.00   25
 45  \w     65.00  91.00   1.00    2.00    --   95.80  77.00 150.00   26
 46  \w     64.00  90.00   1.00    2.00    --   95.80  82.00 -90.00   26
 47  \w     75.00 158.00   1.00    2.00    --   95.80  45.00-150.00   83
 48  \w     75.00 108.00   1.00    2.00    --   95.80  45.00 -60.00   33
 49  \w    116.00 146.00   1.00    2.00    --   95.80  45.00 -60.00   30
 50  \w     75.00 101.00   1.00    2.00    --   95.80  45.00 120.00   26
 51  \w     63.00  89.00   1.00    2.00    --   95.80  82.00-180.00   26
 52  \w     76.00 127.00   1.00    2.00    --   95.80  45.00 -30.00   51
 53  \w      8.00 120.00   1.00    2.00    --   95.80 -61.00 150.00  112
 54  \w     65.00  90.00   1.00    2.00    --   95.80  77.00 -60.00   25
 55  \w     75.00 100.00   1.00    2.00    --   95.80  45.00-120.00   25
 56  \w     71.00 173.00   1.00    2.00    --   95.80  61.00  60.00  102
 57  \w      7.00 120.00   1.00    2.00    --   95.80 -61.00 -60.00  113
 58  \w     63.00  88.00   1.00    2.00    --   95.80  82.00-120.00   25
 59  \w    160.00 185.00   1.00    2.00    --   95.80  82.00-120.00   25
 60  \w     63.00  89.00   1.00    2.00    --   95.80  82.00  90.00   26
 61  \w     19.00 128.00   1.00    2.00    --   95.80 -82.00 150.00  109
 62  \w     71.00 110.00   1.00    2.00    --   95.80 -82.00  60.00   39
 63  \w    115.00 185.00   1.00    2.00    --   95.80  82.00-150.00   70
 64  \w     10.00 127.00   1.00    2.00    --   95.80 -82.00 -60.00  117
 65  \w     69.00  95.00   1.00    2.00    --   95.80  70.00 150.26   26
 66  \w    140.00 165.00   1.00    2.00    --   95.80  43.00-161.33   25
 67  \w     75.00 168.00   1.00    2.00    --   95.80  46.00  32.25   93
 68  \w     74.00 183.00   1.00    2.00    --   95.80  49.00   0.17  109
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0093381000
_diffrn_orient_matrix_UB_12      -0.0465977000
_diffrn_orient_matrix_UB_13      -0.0624648000
_diffrn_orient_matrix_UB_21      -0.0432577000
_diffrn_orient_matrix_UB_22      0.1295177000
_diffrn_orient_matrix_UB_23      -0.0242329000
_diffrn_orient_matrix_UB_31      0.1644554000
_diffrn_orient_matrix_UB_32      0.0367936000
_diffrn_orient_matrix_UB_33      0.0062097000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0811
_diffrn_reflns_av_unetI/netI     0.0523
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            52769
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.048
_diffrn_reflns_theta_max         67.048
_diffrn_reflns_theta_min         3.864
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.537
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.13808
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
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    1.396
_exptl_crystal_description       block
_exptl_crystal_F_000             984
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.36
_exptl_crystal_size_min          0.26
_refine_diff_density_max         0.275
_refine_diff_density_min         -0.170
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 3120 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.009(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     579
_refine_ls_number_reflns         8033
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0397
_refine_ls_R_factor_gt           0.0359
_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^)+(0.0524P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0942
_refine_ls_wR_factor_ref         0.0968
_reflns_Friedel_coverage         0.889
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                7268
_reflns_number_total             8033
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04474b2.cif
_cod_data_source_block           exp_3367
_cod_depositor_comments
'Adding full bibliography for 1570174--1570176.cif.'
_cod_database_code               1570176
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.558
_shelx_estimated_absorpt_t_min   0.415
_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 Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C34(H34A,H34B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5), C7(H7), C13(H13), C14(H14), C15(H15),
 C16(H16), C17(H17), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C25(H25),
  C26(H26), C28(H28), C29(H29), C31(H31), C37(H37), C38(H38), C39(H39),
 C40(H40), C41(H41), C43(H43), C44(H44), C45(H45), C46(H46), C47(H47)
2.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C48(H48A,H48B,H48C)
;
_shelx_res_checksum              18924
_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 5.062
_oxdiff_exptl_absorpt_empirical_full_min 0.487