Photocatalytic enantioselective Minisci reaction of β-carbolines and application to natural product synthesis.
Luo, Mu-Peng; Gu, Yi-Jie; Wang, Shou-Guo; Chemical science 14 (2023) 251–256; doi:10.1039/d2sc05313f

data_1568016
_publ_section_title
;
 Photocatalytic enantioselective Minisci reaction of &#x3b2;-carbolines
 and application to natural product synthesis.
;
_journal_issue                   2
_journal_name_full               'Chemical science'
_journal_page_first              251
_journal_page_last               256
_journal_paper_doi               10.1039/d2sc05313f
_journal_volume                  14
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H21 N3 O2, 0.311(C H2 Cl2)'
_chemical_formula_sum            'C22.31 H21.62 Cl0.62 N3 O2'
_chemical_formula_weight         385.85
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-10-21
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-10-27 deposited with the CCDC.	2022-11-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.6467(11)
_cell_length_b                   14.7349(12)
_cell_length_c                   18.2076(14)
_cell_measurement_reflns_used    9174
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      73.43
_cell_measurement_theta_min      4.22
_cell_volume                     3929.5(5)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Apex3 (Bruker 2018)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT 2014'
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Bruker PHOTON III area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34138
_diffrn_reflns_av_R_equivalents  0.0631
_diffrn_reflns_av_unetI/netI     0.0231
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            171070
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         73.647
_diffrn_reflns_theta_min         3.357
_diffrn_source                   'microfocus Metaljet'
_diffrn_source_current           3.0
_diffrn_source_power             0.20958
_diffrn_source_type              'Incoatec Metaljet'
_diffrn_source_voltage           69.86
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.935
_exptl_absorpt_correction_T_max  0.7537
_exptl_absorpt_correction_T_min  0.6450
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1270 before and 0.0674 after correction.
The Ratio of minimum to maximum transmission is 0.8558.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.304
_exptl_crystal_description       block
_exptl_crystal_F_000             1625
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.296
_refine_diff_density_min         -0.376
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details
;
 Flack x determined using 4839 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.025(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     543
_refine_ls_number_reflns         12007
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0385
_refine_ls_R_factor_gt           0.0364
_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^)+(0.0661P)^2^+0.5588P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1036
_refine_ls_wR_factor_ref         0.1048
_reflns_Friedel_coverage         0.822
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                11351
_reflns_number_total             12007
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc05313f2.cif
_cod_data_source_block           cxy5030_0m
_cod_depositor_comments          'Adding full bibliography for 1568016.cif.'
_cod_database_code               1568016
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.850
_shelx_estimated_absorpt_t_min   0.793
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C38-C25 = C38A-C25A
 1.54 with sigma of 0.02
 N4-C25 \\sim N4-C25A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C25A) \\sim Ueq, Uanis(C38A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C25) = Uanis(C25A)
Uanis(C39) = Uanis(C39A)
Uanis(C38) = Uanis(C38A)
Uanis(C42A) = Uanis(C42)
Uanis(C44A) = Uanis(C44)
Uanis(C43A) = Uanis(C43)
Uanis(C40) = Uanis(C40A)
Uanis(C41) = Uanis(C41A)
4. Others
 Sof(H4B)=Sof(C38A)=Sof(H38C)=Sof(H38D)=Sof(C39A)=Sof(C40A)=Sof(H40A)=
 Sof(C41A)=Sof(H41A)=Sof(C42A)=Sof(H42A)=Sof(C43A)=Sof(H43A)=Sof(C44A)=
 Sof(H44A)=Sof(C25A)=Sof(H25A)=1-FVAR(1)
 Sof(H4A)=Sof(C42)=Sof(H42)=Sof(C41)=Sof(H41)=Sof(C40)=Sof(H40)=Sof(C39)=
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(C25)=Sof(H25)=Sof(C43)=Sof(H43)=Sof(C44)=
 Sof(H44)=Sof(Cl1)=Sof(Cl2)=Sof(C1)=Sof(H1A)=Sof(H1B)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C3(H3A), C25(H25), C25A(H25A)
5.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C38(H38A,H38B), C1(H1A,H1B), C38A(H38C,H38D)
5.c Aromatic/amide H refined with riding coordinates:
 N3(H3), N1(H1), C20(H20), C19(H19), C18(H18), C11(H11), C21(H21), C22(H22),
 C5(H5), C6(H6A), C15(H15), C14(H14), N4(H4A), N4(H4B), N6(H6), C42(H42),
 C41(H41), C40(H40), C33(H33), C36(H36), C37(H37), C27(H27), C28(H28), C43(H43),
  C44(H44), C40A(H40A), C41A(H41A), C42A(H42A), C43A(H43A), C44A(H44A)
5.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C23(H23A,H23B,H23C), C35(H35A,H35B,H35C), C45(H45A,H45B,
 H45C)
;
_shelx_res_checksum              70315
_olex2_submission_special_instructions 'No special instructions were received'