Enantio- and diastereodivergent synthesis of fused indolizines enabled by synergistic Cu/Ir catalysis.
Zhu, Bing-Ke; Xu, Hui; Xiao, Lu; Chang, Xin; Wei, Liang; Teng, Huailong; Dang, Yanfeng; Dong, Xiu-Qin; Wang, Chun-Jiang; Chemical science 14 (2023) 4134–4142; doi:10.1039/d3sc00118k

data_1568720
_publ_section_title
;
 Enantio- and diastereodivergent synthesis of fused indolizines enabled by
 synergistic Cu/Ir catalysis.
;
_journal_issue                   15
_journal_name_full               'Chemical science'
_journal_page_first              4134
_journal_page_last               4142
_journal_paper_doi               10.1039/d3sc00118k
_journal_volume                  14
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C27 H26 N2 O2'
_chemical_formula_sum            'C27 H26 N2 O2'
_chemical_formula_weight         410.50
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-03-23
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-11-22 deposited with the CCDC.	2023-03-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.94728(4)
_cell_length_b                   13.79687(7)
_cell_length_c                   22.55057(13)
_cell_measurement_reflns_used    19587
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.6390
_cell_measurement_theta_min      3.2160
_cell_volume                     2161.49(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -68.00 -25.00   0.50    0.50    --    0.00 -46.00-155.00   86
  2  \w    -19.00  27.00   0.50    0.50    --    0.00  46.00  -6.00   92
  3  \w     23.00 107.00   0.50    0.50    --   94.60 -46.00-155.00  168
  4  \w     76.00 174.00   0.50    0.50    --   94.60  46.00  -6.00  196
  5  \w    -33.00  31.00   0.50    0.50    --    0.00 -82.00-180.00  128
  6  \w    -43.00  13.00   0.50    0.50    --    0.00 -19.00  90.00  112
  7  \w     35.00  81.00   0.50    0.50    --    0.00  38.00 120.00   92
  8  \w     31.00  57.00   0.50    0.50    --    0.00  46.00  -6.00   52
  9  \w     51.00 113.00   0.50    0.50    --   94.60 -45.00   0.00  124
 10  \w     75.00 101.00   0.50    0.50    --   94.60  45.00  90.00   52
 11  \w     71.00  97.00   0.50    0.50    --   94.60  15.00  90.00   52
 12  \w     75.00 148.00   0.50    0.50    --   94.60  60.00 109.54  146
 13  \w    123.00 184.00   0.50    0.50    --   94.60  30.00 150.00  122
 14  \w    153.00 179.00   0.50    0.50    --   94.60  60.00 109.54   52
 15  \w     86.00 111.00   0.50    0.50    --   94.60  45.00  60.00   50
 16  \w      6.00  63.00   0.50    0.50    --   94.60 -61.00-150.00  114
 17  \w     78.00 117.00   0.50    0.50    --   94.60 -61.00-150.00   78
 18  \w     71.00  97.00   0.50    0.50    --   94.60  61.00  90.00   52
 19  \w     42.00 106.00   0.50    0.50    --   94.60 -61.00   0.00  128
 20  \w     15.00  40.00   0.50    0.50    --   94.60 -61.00   0.00   50
 21  \w     81.00 137.00   0.50    0.50    --   94.60  45.00 150.00  112
 22  \w     71.00  97.00   0.50    0.50    --   94.60  61.00  60.00   52
 23  \w     84.00 179.00   0.50    0.50    --   94.60  30.00 -60.00  190
 24  \w     16.00  99.00   0.50    0.50    --   94.60 -30.00  90.00  166
 25  \w     74.00 149.00   0.50    0.50    --   94.60  49.00  96.64  150
 26  \w     81.00 150.00   0.50    0.50    --   94.60  30.00  90.00  138
 27  \w     84.00 110.00   0.50    0.50    --   94.60  77.00 120.00   52
 28  \w     75.00 100.00   0.50    0.50    --   94.60  53.00 110.01   50
 29  \w     74.00  99.00   0.50    0.50    --   94.60  61.00 120.00   50
 30  \w    128.00 153.00   0.50    0.50    --   94.60  82.00-180.00   50
 31  \w    127.00 153.00   0.50    0.50    --   94.60  15.00  90.00   52
 32  \w     20.00  87.00   0.50    0.50    --   94.60 -30.00  30.00  134
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.2162523000
_diffrn_orient_matrix_UB_12      0.0100362000
_diffrn_orient_matrix_UB_13      -0.0137695000
_diffrn_orient_matrix_UB_21      0.0481134000
_diffrn_orient_matrix_UB_22      -0.0632986000
_diffrn_orient_matrix_UB_23      0.0543019000
_diffrn_orient_matrix_UB_31      -0.0095112000
_diffrn_orient_matrix_UB_32      -0.0914406000
_diffrn_orient_matrix_UB_33      -0.0390990000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0347
_diffrn_reflns_av_unetI/netI     0.0204
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            26849
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.918
_diffrn_reflns_theta_min         3.756
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.629
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53721
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.261
_exptl_crystal_description       block
_exptl_crystal_F_000             872
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.186
_refine_diff_density_min         -0.124
_refine_diff_density_rms         0.030
_refine_ls_abs_structure_details
;
 Flack x determined using 1773 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.08(6)
_refine_ls_extinction_coef       0.0022(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     287
_refine_ls_number_reflns         4335
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0268
_refine_ls_R_factor_gt           0.0263
_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^)+(0.0316P)^2^+0.4883P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0668
_refine_ls_wR_factor_ref         0.0673
_reflns_Friedel_coverage         0.730
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.982
_reflns_number_gt                4251
_reflns_number_total             4335
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc00118k2.cif
_cod_data_source_block           20210323_zbk-2-156
_cod_depositor_comments          'Adding full bibliography for 1568720.cif.'
_cod_database_code               1568720
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.940
_shelx_estimated_absorpt_t_min   0.787
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.a Ternary CH refined with riding coordinates:
 C008(H008), C00I(H00I)
2.b Secondary CH2 refined with riding coordinates:
 C00U(H00S,H00U)
2.c Aromatic/amide H refined with riding coordinates:
 C00A(H00A), C00B(H00B), C00D(H00D), C00G(H00G), C00H(H00H), C00L(H00L),
 C00M(H00M), C00N(H00N), C00O(H00O), C00P(H00P), C00Q(H00Q), C00R(H00R),
 C00T(H00T)
2.d X=CH2 refined with riding coordinates:
 C00K(H00C,H00E)
2.e Idealised Me refined as rotating group:
 C00S(H00F,H00J,H00K), C00V(H00V,H00W,H00X)
;
_shelx_res_checksum              87998
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.906
_oxdiff_exptl_absorpt_empirical_full_min 0.561