Photoredox Asymmetric Nucleophilic Dearomatization of Indoles with Neutral Radicals
Zhang, Yueteng; Ji, Peng; Gao, Feng; Huang, He; Zeng, Fanxun; Wang, Wei; ACS Catalysis 11 (2021) 998–1007; doi:10.1021/acscatal.0c04696

data_4518469
_publ_section_title
;
 Photoredox Asymmetric Nucleophilic Dearomatization of Indoles with
 Neutral Radicals
;
_journal_issue                   2
_journal_name_full               'ACS Catalysis'
_journal_page_first              998
_journal_page_last               1007
_journal_paper_doi               10.1021/acscatal.0c04696
_journal_volume                  11
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C32 H40 I N3 O5 S'
_chemical_formula_sum            'C32 H40 I N3 O5 S'
_chemical_formula_weight         705.63
_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             2020-09-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.478(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.5558(19)
_cell_length_b                   12.2352(18)
_cell_length_c                   21.214(3)
_cell_measurement_reflns_used    9033
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      26.372
_cell_measurement_theta_min      2.32
_cell_volume                     3257.9(8)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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      100.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0316
_diffrn_reflns_av_unetI/netI     0.0298
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            75189
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.415
_diffrn_reflns_theta_min         0.960
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.090
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6772
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0709 before and 0.0549 after correction. The Ratio of minimum to maximum transmission is 0.9085. The \l/2 correction factor is 0.00150.'
_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    1.439
_exptl_crystal_description       plate
_exptl_crystal_F_000             1448
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.05
_refine_diff_density_max         2.547
_refine_diff_density_min         -0.533
_refine_diff_density_rms         0.070
_refine_ls_abs_structure_details
;
 Flack x determined using 5573 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.032(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     846
_refine_ls_number_reflns         13370
_refine_ls_number_restraints     72
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0355
_refine_ls_R_factor_gt           0.0322
_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^)+(0.0456P)^2^+1.7607P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0793
_refine_ls_wR_factor_ref         0.0817
_reflns_Friedel_coverage         0.905
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                12524
_reflns_number_total             13370
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c04696_si_003.cif
_cod_data_source_block           mo_yz_13_178wq_0m
_cod_database_code               4518469
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.948
_shelx_estimated_absorpt_t_min   0.722
_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
 C29C-C31C
 1.51 with sigma of 0.002
 C29C-C32C
 1.51 with sigma of 0.002
 C29C-C30C
 1.51 with sigma of 0.002
 C29B-C31B
 1.51 with sigma of 0.002
 C29B-C32B
 1.51 with sigma of 0.002
 C29B-C30B
 1.51 with sigma of 0.002
 C29C-O4C
 1.5 with sigma of 0.002
 C29B-O4B
 1.5 with sigma of 0.002
3. Rigid bond restraints
 C32B, C29B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C28C, N1B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C28C, O4C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O5C, C28C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C29C, O4C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C29C, C30C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C29C, C31C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C31B, C29B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C32C, C29C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
C29C \\sim C30C: within 1.7A with sigma of 0.004 and sigma for terminal atoms
of 0.008
C32C \\sim C29C: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
Uanis(C28C) \\sim Ueq, Uanis(O5C) \\sim Ueq, Uanis(O4C) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C29C) \\sim Ueq, Uanis(C31C) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C30C) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C32C) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
5. Others
 Sof(I1C)=1-FVAR(1)
 Sof(I1B)=FVAR(1)
 Sof(C28C)=Sof(O5C)=Sof(O4C)=Sof(C32C)=Sof(H32D)=Sof(H32E)=Sof(H32F)=Sof(C29C)=
 Sof(C31C)=Sof(H31D)=Sof(H31E)=Sof(H31F)=Sof(C30C)=Sof(H30D)=Sof(H30E)=
 Sof(H30F)=1-FVAR(2)
 Sof(O4B)=Sof(O5B)=Sof(C28B)=Sof(C31B)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C29B)=
 Sof(C30B)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C32B)=Sof(H32A)=Sof(H32B)=
 Sof(H32C)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C18A(H18A), C7B(H7B), C8A(H8A), C8B(H8B), C18B(H18B), C7A(H7A), C20B(H20B),
 C20A(H20A)
6.b Secondary CH2 refined with riding coordinates:
 C19A(H19C,H19D), C9B(H9BA,H9BB), C9A(H9AA,H9AB), C19B(H19A,H19B), C22B(H22A,
 H22B), C21B(H21A,H21B), C21A(H21C,H21D), C24A(H24C,H24D), C24B(H24A,H24B),
 C22A(H22C,H22D)
6.c Aromatic/amide H refined with riding coordinates:
 C15A(H15A), C2A(H2A), C5A(H5A), C11B(H11B), C11A(H11A), C15B(H15B),
 C14B(H14B), C12B(H12B), C5B(H5B), C6A(H6A), C12A(H12A), C13A(H13A), C14A(H14A),
  C6B(H6B), C2B(H2B), C13B(H13B)
6.d Idealised Me refined as rotating group:
 C27A(H27D,H27E,H27F), C32A(H32G,H32H,H32I), C26B(H26A,H26B,H26C), C16A(H16D,
 H16E,H16F), C16B(H16A,H16B,H16C), C27B(H27A,H27B,H27C), C31A(H31G,H31H,H31I),
 C26A(H26D,H26E,H26F), C30A(H30G,H30H,H30I), C31B(H31A,H31B,H31C), C30B(H30A,
 H30B,H30C), C32B(H32A,H32B,H32C), C32C(H32D,H32E,H32F), C31C(H31D,H31E,H31F),
 C30C(H30D,H30E,H30F)
;
_shelx_res_checksum              80269
_shelx_hkl_checksum              81307
_olex2_submission_special_instructions 'No special instructions were received'