Stereo- and Enantioselective Benzylic C‒H Alkenylation via Photoredox/Nickel Dual Catalysis
Cheng, Xiaokai; Li, Tongtong; Liu, Yuting; Lu, Zhan; ACS Catalysis  (2021) 11059–11065; doi:10.1021/acscatal.1c02851

data_4518966
_publ_section_title
;
 Stereo- and Enantioselective Benzylic C--H Alkenylation via
 Photoredox/Nickel Dual Catalysis
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              11059
_journal_page_last               11065
_journal_paper_doi               10.1021/acscatal.1c02851
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C84 H132 Cl4 N8 Ni2'
_chemical_formula_sum            'C84 H132 Cl4 N8 Ni2'
_chemical_formula_weight         1513.19
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-08-02
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.986(6)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   35.178(6)
_cell_length_b                   10.1527(18)
_cell_length_c                   14.771(3)
_cell_measurement_reflns_used    6319
_cell_measurement_temperature    170(2)
_cell_measurement_theta_max      26.89
_cell_measurement_theta_min      2.46
_cell_volume                     5195.6(17)
_computing_cell_refinement       'SAINT V8.38A (Bruker AXS Inc., 2017)'
_computing_data_collection       'Bruker Instrument Service vV6.2.10'
_computing_data_reduction        'SAINT V8.38A (Bruker AXS Inc., 2017)'
_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 0.993
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device_type  'zju Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0815
_diffrn_reflns_av_unetI/netI     0.1552
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       41
_diffrn_reflns_limit_h_min       -44
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            20820
_diffrn_reflns_point_group_measured_fraction_full 0.964
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.169
_diffrn_reflns_theta_min         2.351
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.503
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.5767
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1214 before and 0.0723 after correction.
The Ratio of minimum to maximum transmission is 0.7736.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    0.967
_exptl_crystal_description       needle
_exptl_crystal_F_000             1632
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.427
_refine_diff_density_min         -0.667
_refine_diff_density_rms         0.068
_refine_ls_abs_structure_details
;
 Flack x determined using 1514 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.014(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     549
_refine_ls_number_reflns         10909
_refine_ls_number_restraints     264
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.1563
_refine_ls_R_factor_gt           0.0700
_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^)+(0.0772P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1514
_refine_ls_wR_factor_ref         0.2091
_reflns_Friedel_coverage         0.817
_reflns_Friedel_fraction_full    0.931
_reflns_Friedel_fraction_max     0.902
_reflns_number_gt                5243
_reflns_number_total             10909
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c02851_si_002.cif
_cod_data_source_block           201011_cxk14106_0m
_cod_original_cell_volume        5195.4(16)
_cod_database_code               4518966
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.980
_shelx_estimated_absorpt_t_min   0.868
_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
 C31-C34 \\sim C31-C34A
 with sigma of 0.02
 C31-C33 \\sim C31-C33A
 with sigma of 0.02
 C31-C32 \\sim C31-C32A
 with sigma of 0.02
 C32-C33 \\sim C33-C34 \\sim C34-C32
 with sigma of 0.02
 C18A-C19A \\sim C19A-C20A \\sim C20A-C18A
 with sigma of 0.02
 C36A-C37A \\sim C37A-C38A \\sim C38A-C36A
 with sigma of 0.02
 C35-C37 \\sim C35-C37A
 with sigma of 0.02
 C35-C38 \\sim C35-C38A
 with sigma of 0.02
 C35-C36 \\sim C35-C36A
 with sigma of 0.02
 C17-C19 \\sim C17-C19A
 with sigma of 0.02
 C17-C20 \\sim C17-C20A
 with sigma of 0.02
 C17-C18 \\sim C17-C18A
 with sigma of 0.02
 C21-C23 \\sim C21-C23A
 with sigma of 0.02
 C21-C22 \\sim C21-C22A
 with sigma of 0.02
 C21-C24 \\sim C21-C24A
 with sigma of 0.02
3. Rigid bond restraints
 N1, C3
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C29, C30
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
C31 \\sim C33 \\sim C32 \\sim C33A \\sim C32A \\sim C34 \\sim C34A: within 1.7A
with sigma of 0.01 and sigma for terminal atoms of 0.02
C35 \\sim C38A \\sim C38 \\sim C37A \\sim C37 \\sim C36A \\sim C36: within 1.7A
with sigma of 0.01 and sigma for terminal atoms of 0.02
C17 \\sim C20 \\sim C20A \\sim C19 \\sim C19A \\sim C18 \\sim C18A: within 1.7A
with sigma of 0.01 and sigma for terminal atoms of 0.02
C21 \\sim C24 \\sim C24A \\sim C22 \\sim C22A \\sim C23 \\sim C23A: within 1.7A
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C24A) = Uanis(C24)
5. Others
 Sof(C34A)=Sof(H34D)=Sof(H34E)=Sof(H34F)=Sof(C33A)=Sof(H33D)=Sof(H33E)=
 Sof(H33F)=Sof(C32A)=Sof(H32D)=Sof(H32E)=Sof(H32F)=1-FVAR(1)
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=
 Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(1)
 Sof(C37A)=Sof(H37D)=Sof(H37E)=Sof(H37F)=Sof(C38A)=Sof(H38D)=Sof(H38E)=
 Sof(H38F)=Sof(C36A)=Sof(H36D)=Sof(H36E)=Sof(H36F)=1-FVAR(2)
 Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=
 Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=FVAR(2)
 Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C18A)=Sof(H18D)=Sof(H18E)=
 Sof(H18F)=Sof(C19A)=Sof(H19D)=Sof(H19E)=Sof(H19F)=1-FVAR(3)
 Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=FVAR(3)
 Sof(C22A)=Sof(H22D)=Sof(H22E)=Sof(H22F)=Sof(C23A)=Sof(H23D)=Sof(H23E)=
 Sof(H23F)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=1-FVAR(4)
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C39(H39), C1(H1), C7(H7), C5(H5)
6.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C41(H41A,H41B), C6(H6A,H6B), C9(H9A,H9B)
6.c Me refined with riding coordinates:
 C8(H8A,H8B,H8C), C40(H40A,H40B,H40C), C10(H10A,H10B,H10C), C37(H37A,H37B,
 H37C), C38(H38A,H38B,H38C), C42(H42A,H42B,H42C), C23(H23A,H23B,H23C), C34(H34A,
 H34B,H34C), C22(H22A,H22B,H22C), C36(H36A,H36B,H36C), C33(H33A,H33B,H33C),
 C32(H32A,H32B,H32C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C18(H18A,H18B,
 H18C), C24(H24A,H24B,H24C), C34A(H34D,H34E,H34F), C33A(H33D,H33E,H33F),
 C32A(H32D,H32E,H32F), C37A(H37D,H37E,H37F), C38A(H38D,H38E,H38F), C36A(H36D,
 H36E,H36F), C20A(H20D,H20E,H20F), C18A(H18D,H18E,H18F), C19A(H19D,H19E,H19F),
 C22A(H22D,H22E,H22F), C23A(H23D,H23E,H23F), C24A(H24D,H24E,H24F)
6.d Aromatic/amide H refined with riding coordinates:
 C30(H30), C26(H26), C14(H14), C16(H16), C12(H12), C28(H28)
;
_shelx_res_checksum              37245
_shelx_hkl_checksum              35969
_shelx_fab_checksum              77554
_olex2_submission_special_instructions 'No special instructions were received'