Cu/Chiral Phosphoric Acid-Catalyzed Asymmetric Three-Component Radical-Initiated 1,2-Dicarbofunctionalization of Alkenes.
Lin, Jin-Shun; Li, Tao-Tao; Liu, Ji-Ren; Jiao, Guan-Yuan; Gu, Qiang-Shuai; Cheng, Jiang-Tao; Guo, Yu-Long; Hong, Xin; Liu, Xin-Yuan; Journal of the American Chemical Society 141 (2019) 1074–1083; doi:10.1021/jacs.8b11736

data_4133617
_publ_section_title
;
 Cu/Chiral Phosphoric Acid-Catalyzed Asymmetric Three-Component
 Radical-Initiated 1,2-Dicarbofunctionalization of Alkenes.
;
_journal_issue                   2
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              1074
_journal_page_last               1083
_journal_paper_doi               10.1021/jacs.8b11736
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C24 H19 F3 N2 O4, C H Cl3'
_chemical_formula_sum            'C25 H20 Cl3 F3 N2 O4'
_chemical_formula_weight         575.78
_space_group_crystal_system      hexagonal
_space_group_IT_number           168
_space_group_name_Hall           'P 6'
_space_group_name_H-M_alt        'P 6'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-02-08
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   22.0755(4)
_cell_length_b                   22.0755(4)
_cell_length_c                   10.0326(2)
_cell_measurement_reflns_used    9918
_cell_measurement_temperature    100
_cell_measurement_theta_max      65.310
_cell_measurement_theta_min      4.005
_cell_volume                     4234.14(14)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker PHOTO 100 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker PHOTO 100 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0611
_diffrn_reflns_av_unetI/netI     0.0356
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            29278
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        65.305
_diffrn_reflns_theta_max         65.305
_diffrn_reflns_theta_min         2.311
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.406
_exptl_absorpt_correction_T_max  0.7526
_exptl_absorpt_correction_T_min  0.4777
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1008 before and 0.0663 after correction. The Ratio of minimum to maximum transmission is 0.6347. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.355
_exptl_crystal_description       prism
_exptl_crystal_F_000             1764
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.45
_exptl_crystal_size_min          0.38
_refine_diff_density_max         1.457
_refine_diff_density_min         -0.791
_refine_diff_density_rms         0.097
_refine_ls_abs_structure_details
;
 Flack x determined using 1876 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.08(3)
_refine_ls_extinction_coef       0.0022(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     344
_refine_ls_number_reflns         4840
_refine_ls_number_restraints     19
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0863
_refine_ls_R_factor_gt           0.0810
_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^)+(0.1707P)^2^+3.2931P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2259
_refine_ls_wR_factor_ref         0.2342
_reflns_Friedel_coverage         0.878
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                4433
_reflns_number_total             4840
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b11736_si_003.cif
_cod_data_source_block           cu_cxy0304_0m
_cod_original_cell_volume        4234.14(18)
_cod_database_code               4133617
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 O3-N2 \\sim O3-N2A \\sim O4-N2A \\sim O4A-N2
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(N2) \\sim Ueq, Uanis(O4A) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(O4A) = Uanis(O4)
Uanis(N2A) = Uanis(N2)
4. Others
 Sof(N2)=Sof(O4A)=1-FVAR(1)
 Sof(O4)=Sof(N2A)=FVAR(1)
5.a Riding coordinates:
 N1(H1A)
5.b Ternary CH refined with riding coordinates:
 C25(H25)
5.c Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B)
5.d Aromatic/amide H refined with riding coordinates:
 C1(H1B), C2(H2), C4(H4), C5(H5), C11(H11), C12(H12), C14(H14), C15(H15),
 C17(H17), C19(H19), C20(H20), C22(H22)
5.e Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C)
5.f Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              64009
_shelx_hkl_checksum              70550
_shelx_fab_checksum              33308
_olex2_submission_special_instructions 'No special instructions were received'