Stereodivergent Construction of Tertiary Fluorides in Vicinal Stereogenic Pairs by Allylic Substitution with Iridium and Copper Catalysts.
He, Zhi-Tao; Jiang, Xingyu; Hartwig, John F.; Journal of the American Chemical Society 141 (2019) 13066–13073; doi:10.1021/jacs.9b04440

data_4127849
_publ_section_title
;
 Stereodivergent Construction of Tertiary Fluorides in Vicinal Stereogenic
 Pairs by Allylic Substitution with Iridium and Copper Catalysts.
;
_journal_issue                   33
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13066
_journal_page_last               13073
_journal_paper_doi               10.1021/jacs.9b04440
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H19 F N2 O S'
_chemical_formula_sum            'C20 H19 F N2 O S'
_chemical_formula_weight         354.43
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-03-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.30661(5)
_cell_length_b                   8.76884(7)
_cell_length_c                   31.4352(2)
_cell_measurement_reflns_used    24574
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      78.7740
_cell_measurement_theta_min      5.1840
_cell_volume                     1738.42(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -13.00  71.00   0.50    0.50    --    0.00  59.00  -6.00  168
  2  \w   -115.00 -31.00   0.50    0.50    -- -100.00  64.00 147.00  168
  3  \w   -169.00 -85.00   0.50    0.50    -- -100.00 -64.00  11.00  168
  4  \w   -176.00 -86.00   0.50    0.50    -- -100.00-110.00 133.00  180
  5  \w     30.00 112.00   0.50    0.50    --  106.00-110.00 133.00  164
  6  \w     93.00 177.00   0.50    0.50    --  106.00  59.00  -6.00  168
  7  \w    -15.00  31.00   0.50    0.50    --    0.00 -99.00 -30.00   92
  8  \w    -15.00  31.00   0.50    0.50    --    0.00 -99.00  60.00   92
  9  \w    -15.00  31.00   0.50    0.50    --    0.00 -99.00   0.00   92
 10  \w   -176.00 -86.00   0.50    0.50    -- -100.00-111.00  90.00  180
 11  \w    -72.00 -23.00   0.50    0.50    -- -100.00  30.00-180.00   98
 12  \w    -72.00 -23.00   0.50    0.50    -- -100.00  30.00  60.00   98
 13  \w    -72.00 -23.00   0.50    0.50    -- -100.00  30.00  90.00   98
 14  \w     27.00 113.00   0.50    0.50    --  106.00 -15.00-150.00  172
 15  \w     31.00  74.00   0.50    0.50    --  106.00 -45.00-180.00   86
 16  \w     31.00  74.00   0.50    0.50    --  106.00 -45.00  60.00   86
 17  \w     30.00 109.00   0.50    0.50    --  106.00 -94.00   0.00  158
 18  \w     29.00 114.00   0.50    0.50    --  106.00   0.00-180.00  170
 19  \w     99.00 178.00   0.50    0.50    --  106.00  15.00-180.00  158
 20  \w     29.00  66.00   0.50    0.50    --  106.00 -30.00-150.00   74
 21  \w    -13.00  72.00   0.50    0.50    --    0.00  57.00 120.00  170
 22  \w    -15.00  31.00   0.50    0.50    --    0.00 -99.00 -90.00   92
 23  \w    -45.00  20.00   0.50    0.50    --    0.00 -77.00-180.00  130
 24  \w   -171.00 -87.00   0.50    0.50    -- -100.00 -59.00-146.00  168
 25  \w   -170.00 -86.00   0.50    0.50    -- -100.00 -61.00-120.00  168
 26  \w   -172.00 -80.00   0.50    0.50    -- -100.00 -77.00 -60.00  184
 27  \w   -170.00-145.00   0.50    0.50    -- -100.00 -61.00 120.00   50
 28  \w   -170.00 -86.00   0.50    0.50    -- -100.00 -61.00 150.00  168
 29  \w     99.00 178.00   0.50    0.50    --  106.00  15.00  60.00  158
 30  \w     99.00 178.00   0.50    0.50    --  106.00  15.00 -30.00  158
 31  \w     30.00 112.00   0.50    0.50    --  106.00-111.00   0.00  164
 32  \w     30.00 109.00   0.50    0.50    --  106.00 -94.00-180.00  158
 33  \w     29.00 114.00   0.50    0.50    --  106.00   0.00 -30.00  170
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom DW system, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0331837000
_diffrn_orient_matrix_UB_12      -0.0296677000
_diffrn_orient_matrix_UB_13      -0.0478437000
_diffrn_orient_matrix_UB_21      -0.1789678000
_diffrn_orient_matrix_UB_22      0.1196245000
_diffrn_orient_matrix_UB_23      -0.0007676000
_diffrn_orient_matrix_UB_31      0.1629389000
_diffrn_orient_matrix_UB_32      0.1251799000
_diffrn_orient_matrix_UB_33      -0.0105943000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0360
_diffrn_reflns_av_unetI/netI     0.0142
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            30608
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        74.000
_diffrn_reflns_theta_max         74.504
_diffrn_reflns_theta_min         5.237
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.824
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75247
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.354
_exptl_crystal_description       block
_exptl_crystal_F_000             744
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.288
_refine_diff_density_min         -0.176
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 1432 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.009(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     281
_refine_ls_number_reflns         3552
_refine_ls_number_restraints     186
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0279
_refine_ls_R_factor_gt           0.0275
_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^)+(0.0278P)^2^+0.6488P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0672
_refine_ls_wR_factor_ref         0.0675
_reflns_Friedel_coverage         0.705
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                3496
_reflns_number_total             3552
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b04440_si_002.cif
_cod_data_source_block           ent-3m
_cod_database_code               4127849
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C N O S F H'
_shelx_estimated_absorpt_t_max   0.898
_shelx_estimated_absorpt_t_min   0.669
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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. Rigid bond restraints
 N1A, N1B, S1A, S1B, C1A, C1B, C2A, C2B, C3A, C3B, C4A, C4B, C5A, C5B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
N1A \\sim N1B \\sim S1A \\sim S1B \\sim C1A \\sim C1B \\sim C2A \\sim C2B \\sim
C3A \\sim C3B \\sim C4A \\sim C4B \\sim C5A \\sim C5B: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
Uanis(N1A) = Uanis(N1B)
Uanis(C1A) = Uanis(C1B)
4. Others
 Sof(C1B)=Sof(C2B)=Sof(H2B)=Sof(C3B)=Sof(H3B)=Sof(C4B)=Sof(H4B)=Sof(C5B)=
 Sof(H5B)=1-FVAR(1)
 Sof(C1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=
 Sof(H5A)=FVAR(1)
 Sof(S1B)=Sof(N1B)=1-FVAR(2)
 Sof(S1A)=Sof(N1A)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C12(H12)
5.b Aromatic/amide H refined with riding coordinates:
 C2A(H2A), C2B(H2B), C3A(H3A), C4A(H4A), C3B(H3B), C4B(H4B), C5A(H5A),
 C5B(H5B), C13(H13), C16(H16), C17(H17), C18(H18), C19(H19), C20(H20)
5.c X=CH2 refined with riding coordinates:
 C14(H14A,H14B)
5.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C)
;
_shelx_res_checksum              30867
_shelx_hkl_checksum              87786
_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 2.477
_oxdiff_exptl_absorpt_empirical_full_min 0.602