Enantioselective Three-Component Fluoroalkylarylation of Unactivated Olefins through Nickel-Catalyzed Cross-Electrophile Coupling.
Tu, Hai-Yong; Wang, Fang; Huo, Liping; Li, Yuanbo; Zhu, Shengqing; Zhao, Xian; Li, Huan; Qing, Feng-Ling; Chu, Lingling; Journal of the American Chemical Society 142 (2020) 9604–9611; doi:10.1021/jacs.0c03708

data_4134971
_publ_section_title
;
 Enantioselective Three-Component Fluoroalkylarylation of Unactivated
 Olefins through Nickel-Catalyzed Cross-Electrophile Coupling.
;
_journal_issue                   21
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9604
_journal_page_last               9611
_journal_paper_doi               10.1021/jacs.0c03708
_journal_volume                  142
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C14 H12 Br F9 O2 S'
_chemical_formula_sum            'C14 H12 Br F9 O2 S'
_chemical_formula_weight         495.21
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-05-06
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.287(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.7339(6)
_cell_length_b                   46.854(5)
_cell_length_c                   6.9754(7)
_cell_measurement_reflns_used    8330
_cell_measurement_temperature    298.08
_cell_measurement_theta_max      65.189
_cell_measurement_theta_min      5.665
_cell_volume                     1862.7(3)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      298.08
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0382
_diffrn_reflns_av_unetI/netI     0.0432
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       54
_diffrn_reflns_limit_k_min       -55
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            18034
_diffrn_reflns_point_group_measured_fraction_full 0.959
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        66.698
_diffrn_reflns_theta_max         66.698
_diffrn_reflns_theta_min         1.886
_exptl_absorpt_coefficient_mu    4.966
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.5460
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1386 before and 0.0477 after correction.
The Ratio of minimum to maximum transmission is 0.7253.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.766
_exptl_crystal_description       block
_exptl_crystal_F_000             976
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.353
_refine_diff_density_min         -0.368
_refine_diff_density_rms         0.072
_refine_ls_abs_structure_details
;
 Flack x determined using 1863 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.023(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     553
_refine_ls_number_reflns         6318
_refine_ls_number_restraints     1012
_refine_ls_restrained_S_all      1.180
_refine_ls_R_factor_all          0.0857
_refine_ls_R_factor_gt           0.0599
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0891P)^2^+2.0440P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1517
_refine_ls_wR_factor_ref         0.1694
_reflns_Friedel_coverage         0.923
_reflns_Friedel_fraction_full    0.933
_reflns_Friedel_fraction_max     0.933
_reflns_number_gt                4850
_reflns_number_total             6318
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c03708_si_002.cif
_cod_data_source_block           cu_ht6110br_0m_a
_cod_depositor_comments          'Adding full bibliography for 4134971.cif.'
_cod_database_code               4134971
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.637
_shelx_estimated_absorpt_t_min   0.437
_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. Restrained distances
 F11-C24 = F10-C24 = F13-C25 = F12B-C25B = F12-C25 = F13B-C25B = F15-C26 =
 F14B-C26B = F14-C26 = F15B-C26B = F16-C27 = F16B-C27B = F18-C27 = F17B-C27B =
 F17-C27 = F18B-C27B
 1.35 with sigma of 0.02
 F2-C10 = F1-C10 = F4-C11 = F3-C11 = F6-C12 = F5-C12 = F8-C13 = F9-C13 = F7-C13
 1.35 with sigma of 0.02
 C11-C10 = C12-C11 = C13-C12 = C9-C10
 1.5 with sigma of 0.02
 C25B-C24 = C25-C24 = C26B-C25B = C26-C25 = C27B-C26B = C27-C26
 1.5 with sigma of 0.02
 F17B-F18B \\sim F16-F18 \\sim F16B-F17B \\sim F18-F17 \\sim F15B-F14B \\sim
F12B-F13B \\sim F11-F10 ~
 F17-F16 \\sim F13-F12 \\sim F15-F14 \\sim F18B-F16B
 with sigma of 0.02
 F9-F8 \\sim F2-F1 \\sim F4-F3 \\sim F6-F5 \\sim F8-F7 \\sim F7-F9
 with sigma of 0.02
 F16-C26 \\sim F14-C25 \\sim F13-C26 \\sim C27-F14 \\sim F12-C26 \\sim C26-F17
\\sim C26-F18 \\sim C27-F15
 \\sim F15-C25 \\sim F11-C25 \\sim C25-F10 \\sim F13-C24 \\sim F12-C24
 with sigma of 0.02
 C25B-F10 \\sim F12B-C26B \\sim F15B-C25B \\sim F17B-C26B \\sim C26B-F16B \\sim
F18B-C26B \\sim F13B-
 C26B \\sim F15B-C27B \\sim F12B-C24 \\sim F14B-C27B \\sim C25B-F11 \\sim
F14B-C25B \\sim F13B-C24
 with sigma of 0.02
 C12-F7 \\sim F6-C13 \\sim C11-F2 \\sim C11-F6 \\sim C11-F1 \\sim C12-F9 \\sim
C10-F4 \\sim C12-F8 \\sim C11-
 F5 \\sim F5-C13 \\sim C10-F3 \\sim F4-C12 \\sim F3-C12
 with sigma of 0.02
3. Rigid bond restraints
 F1, F2, F3, F4, F5, F6, F7, F8, F9, C10, C11, C12, C13
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F10, F14, F12, F15, F13, F18, F17, F16, C24, C25B, C26, C27, F14B, F18B, F15B,
  C27B, F17B, C26B, F16B, C25, F13B, F12B, F11
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
F1 \\sim F2 \\sim F3 \\sim F4 \\sim F5 \\sim F6 \\sim F7 \\sim F8 \\sim F9
\\sim C10 \\sim C11 \\sim C12 \\sim C13: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
F10 \\sim F11 \\sim F14 \\sim F12 \\sim F15 \\sim F13 \\sim F18 \\sim F17 \\sim
F16 \\sim C24 \\sim C25B \\sim C26 \\sim C27 \\sim F14B \\sim F18B \\sim F15B
\\sim C27B \\sim F17B \\sim C26B \\sim F16B \\sim C25 \\sim F13B \\sim F12B:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(F1) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F9) \\sim Ueq, Uanis(F6) \\sim
Ueq, Uanis(F7) \\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(F8) \\sim Ueq, Uanis(F3)
\\sim Ueq, Uanis(F4) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms
of 0.2
Uanis(F2) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(F9) \\sim
Ueq, Uanis(F7) \\sim Ueq, Uanis(F8) \\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(F4)
\\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C12) \\sim Ueq,
Uanis(C11) \\sim Ueq, Uanis(C10) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
5. Rigid body (RIGU) restrains
 C15, C20, C19, C18, C17, C16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1, C2, C3, C4, C5, C6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: F14(0.5) F12(0.5) F15(0.5) F13(0.5) F18(0.5) F17(0.5) F16(0.5)
 C25B(0.5) C26(0.5) C27(0.5) F14B(0.5) F18B(0.5) F15B(0.5) C27B(0.5) F17B(0.5)
 C26B(0.5) F16B(0.5) C25(0.5) F13B(0.5) F12B(0.5)
7.a Riding coordinates:
 C28(H28A,H28B,H28C), C14(H14A,H14B,H14C)
7.b Ternary CH refined with riding coordinates:
 C7(H7), C21(H21)
7.c Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C22(H22A,H22B), C23(H23A,H23B)
7.d Aromatic/amide H refined with riding coordinates:
 C6(H6), C5(H5), C3(H3), C2(H2), C20(H20), C19(H19), C17(H17), C16(H16)
7.e Fitted hexagon refined as free rotating group:
 C1(C6,C5,C4,C3,C2), C15(C20,C19,C18,C17,C16)
;
_shelx_res_checksum              59606
_olex2_submission_special_instructions 'No special instructions were received'