Chiral π-Cu(ii)-catalyzed site-, <i>exo</i>/<i>endo</i>-, and enantioselective dearomative (3 + 2) cycloadditions of isoquinolinium ylides with enamides, dienamides, and a trienamide.
Guo, Weiwei; Huang, Jianhao; Ishihara, Kazuaki; Chemical science 15 (2024) 10926–10934; doi:10.1039/d4sc02946a

data_1571815
_publ_section_title
;
 Chiral &#x3c0;-Cu(ii)-catalyzed site-, <i>exo</i>/<i>endo</i>-, and
 enantioselective dearomative (3 + 2) cycloadditions of isoquinolinium
 ylides with enamides, dienamides, and a trienamide.
;
_journal_issue                   28
_journal_name_full               'Chemical science'
_journal_page_first              10926
_journal_page_last               10934
_journal_paper_doi               10.1039/d4sc02946a
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H19 Br N6 O'
_chemical_formula_sum            'C25 H19 Br N6 O'
_chemical_formula_weight         499.37
_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             2023-07-21
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2024-01-17 deposited with the CCDC.	2024-06-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.686(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.2893(3)
_cell_length_b                   14.1630(4)
_cell_length_c                   10.0325(3)
_cell_measurement_reflns_used    7952
_cell_measurement_temperature    123.15
_cell_measurement_theta_max      30.7380
_cell_measurement_theta_min      2.1200
_cell_volume                     1144.39(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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      123.15
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.893
_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   -105.00  75.00   0.50    5.00    --  -15.00  45.00   0.00  360
  2  \w   -105.00  75.00   0.50    5.00    --  -15.00  45.00  90.00  360
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0488917000
_diffrn_orient_matrix_UB_12      0.0068484000
_diffrn_orient_matrix_UB_13      0.0675495000
_diffrn_orient_matrix_UB_21      -0.0694509000
_diffrn_orient_matrix_UB_22      0.0201735000
_diffrn_orient_matrix_UB_23      0.0192957000
_diffrn_orient_matrix_UB_31      -0.0235822000
_diffrn_orient_matrix_UB_32      -0.0453214000
_diffrn_orient_matrix_UB_33      0.0187664000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0154
_diffrn_reflns_av_unetI/netI     0.0194
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.893
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            9917
_diffrn_reflns_point_group_measured_fraction_full 0.928
_diffrn_reflns_point_group_measured_fraction_max 0.772
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.815
_diffrn_reflns_theta_min         2.089
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.826
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75042
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.449
_exptl_crystal_description       block
_exptl_crystal_F_000             508
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.349
_refine_diff_density_min         -0.751
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
;
 Flack x determined using 2000 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.011(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     300
_refine_ls_number_reflns         5540
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0265
_refine_ls_R_factor_gt           0.0246
_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^)+(0.0462P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0650
_refine_ls_wR_factor_ref         0.0655
_reflns_Friedel_coverage         0.667
_reflns_Friedel_fraction_full    0.852
_reflns_Friedel_fraction_max     0.641
_reflns_number_gt                5185
_reflns_number_total             5540
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02946a2.cif
_cod_data_source_block           20230721-
_cod_depositor_comments          'Adding full bibliography for 1571815.cif.'
_cod_database_code               1571815
_shelx_shelxl_version_number     2018/1
_reflns_odcompleteness_completeness 89.33
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.75
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C00E(H00E), C00G(H00G), C00O(H00O)
2.b Aromatic/amide H refined with riding coordinates:
 C008(H008), C00B(H00B), C00D(H00D), C00H(H00H), C00I(H00I), C00Q(H00Q),
 C00R(H00R), C00T(H00T), C00V(H00V), C00X(H00X)
2.c Idealised Me refined as rotating group:
 C00U(H00A,H00C,H00F), C00W(H00J,H00K,H00L)
;
_shelx_res_checksum              48083
_shelx_hkl_checksum              47333
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.292
_oxdiff_exptl_absorpt_empirical_full_min 0.784