<i>Cinchona</i> Alkaloid Squaramide-Catalyzed Asymmetric Ugi-Type Reaction of Isocyanoacetates with C,N-Cyclic Azomethine Imines: Access to Chiral Oxazole-Substituted Tetrahydroisoquinolines.
Zhao, Zi-Qiang; Zhao, Xiao-Li; Shi, Min; Zhao, Mei-Xin; The Journal of organic chemistry  (2019) –; doi:10.1021/acs.joc.9b01955

data_4033607
_publ_section_title
;
 <i>Cinchona</i> Alkaloid Squaramide-Catalyzed Asymmetric Ugi-Type
 Reaction of Isocyanoacetates with C,N-Cyclic Azomethine Imines: Access to
 Chiral Oxazole-Substituted Tetrahydroisoquinolines.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.9b01955
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C26 H24 Br N3 O4 S'
_chemical_formula_sum            'C26 H24 Br N3 O4 S'
_chemical_formula_weight         554.45
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 116.482(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.8479(2)
_cell_length_b                   10.01910(10)
_cell_length_c                   11.9095(2)
_cell_measurement_reflns_used    18759
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      74.0850
_cell_measurement_theta_min      4.1420
_cell_volume                     1265.39(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 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      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.986
_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    -23.00   5.00   1.00    1.00    --    0.00  57.00  90.00   28
  2  \w     -9.00  18.00   1.00    1.00    --    0.00 -38.00 -30.00   27
  3  \w     24.00  88.00   1.00    1.00    --    0.00  38.00-150.00   64
  4  \w    -22.00  63.00   1.00    1.00    --    0.00  57.00-120.00   85
  5  \w    -19.00  16.00   1.00    1.00    --    0.00  38.00-150.00   35
  6  \w    -19.00  44.00   1.00    1.00    --    0.00  57.00 150.00   63
  7  \w    -84.00 -27.00   1.00    1.00    --    0.00 -38.00 -30.00   57
  8  \w     47.00  87.00   1.00    1.00    --    0.00  38.00  30.00   40
  9  \w      8.00  88.00   1.00    1.00    --    0.00  57.00  90.00   80
 10  \w     19.00  59.00   1.00    1.00    --    0.00  57.00 -30.00   40
 11  \w    -16.00  66.00   1.00    1.00    --    0.00  57.00 -60.00   82
 12  \w    -17.00  44.00   1.00    1.00    --    0.00  38.00  30.00   61
 13  \w    152.00 183.00   1.00    1.00    --   95.80  77.00  30.00   31
 14  \w     65.00  91.00   1.00    1.00    --   95.80  77.00  30.00   26
 15  \w    118.00 185.00   1.00    1.00    --   95.80  60.00 -20.31   67
 16  \w     66.00 185.00   1.00    1.00    --   95.80  74.00 174.89  119
 17  \w     68.00 115.00   1.00    1.00    --   95.80  71.00 145.59   47
 18  \w     71.00  97.00   1.00    1.00    --   95.80  60.00 -20.31   26
 19  \w    128.00 185.00   1.00    1.00    --   95.80  58.00  71.14   57
 20  \w    148.00 174.00   1.00    1.00    --   95.80  65.00 135.01   26
 21  \w     69.00  94.00   1.00    1.00    --   95.80  65.00 135.01   25
 22  \w    100.00 173.00   1.00    1.00    --   95.80  75.00-129.96   73
 23  \w    113.00 181.00   1.00    1.00    --   95.80  61.00   0.00   68
 24  \w     65.00  98.00   1.00    1.00    --   95.80  77.00-120.00   33
 25  \w     35.00 118.00   1.00    1.00    --   95.80 -82.00  30.00   83
 26  \w     72.00 184.00   1.00    1.00    --   95.80  61.00  90.00  112
 27  \w     64.00  90.00   1.00    1.00    --   95.80  82.00-180.00   26
 28  \w     67.00  93.00   1.00    1.00    --   95.80  82.00-120.00   26
 29  \w     64.00  90.00   1.00    1.00    --   95.80  82.00 -30.00   26
 30  \w     77.00 110.00   1.00    1.00    --   95.80  45.00  30.00   33
 31  \w    117.00 183.00   1.00    1.00    --   95.80  77.00 -90.00   66
 32  \w     75.00 120.00   1.00    1.00    --   95.80  45.00-120.00   45
 33  \w     66.00  92.00   1.00    1.00    --   95.80  75.00-129.96   26
 34  \w    134.00 164.00   1.00    1.00    --   95.80  72.00 -62.20   30
 35  \w    158.00 185.00   1.00    1.00    --   95.80  77.00  90.00   27
 36  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  90.00   25
 37  \w     65.00  91.00   1.00    1.00    --   95.80  77.00   0.00   26
 38  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  60.00   25
 39  \w     66.00  92.00   1.00    1.00    --   95.80  82.00 150.00   26
 40  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 -90.00   25
 41  \w     65.00  91.00   1.00    1.00    --   95.80  77.00-150.00   26
 42  \w     75.00 184.00   1.00    1.00    --   95.80  45.00 150.00  109
 43  \w     64.00  90.00   1.00    1.00    --   95.80  82.00 120.00   26
 44  \w     75.00 107.00   1.00    1.00    --   95.80  45.00  60.00   32
 45  \w    140.00 172.00   1.00    1.00    --   95.80  45.00  60.00   32
 46  \w     71.00  97.00   1.00    1.00    --   95.80  61.00   0.00   26
 47  \w     74.00 144.00   1.00    1.00    --   95.80  64.00 -61.30   70
 48  \w     65.00 102.00   1.00    1.00    --   95.80  77.00-180.00   37
 49  \w    149.00 185.00   1.00    1.00    --   95.80  82.00 -60.00   36
 50  \w     64.00  90.00   1.00    1.00    --   95.80  82.00-150.00   26
 51  \w     78.00 107.00   1.00    1.00    --   95.80  30.00   0.00   29
 52  \w     76.00 113.00   1.00    1.00    --   95.80  45.00 -60.00   37
 53  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 -60.00   26
 54  \w     72.00  98.00   1.00    1.00    --   95.80  61.00 120.00   26
 55  \w     66.00 130.00   1.00    1.00    --   95.80  77.00 150.00   64
 56  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 -90.00   26
 57  \w     63.00  89.00   1.00    1.00    --   95.80  82.00   0.00   26
 58  \w    149.00 174.00   1.00    1.00    --   95.80  82.00   0.00   25
 59  \w     67.00  93.00   1.00    1.00    --   95.80  82.00  60.00   26
 60  \w     55.00 123.00   1.00    1.00    --   95.80 -82.00-120.00   68
 61  \w     68.00 126.00   1.00    1.00    --   95.80 -82.00 150.00   58
 62  \w    138.00 181.00   1.00    1.00    --   95.80  45.00  30.00   43
 63  \w      7.00 119.00   1.00    1.00    --   95.80 -82.00  90.00  112
 64  \w     66.00  92.00   1.00    1.00    --   95.80  74.00 -29.93   26
 65  \w     68.00  94.00   1.00    1.00    --   95.80  72.00 -62.20   26
 66  \w     71.00 104.00   1.00    1.00    --   95.80  58.00  71.14   33
 67  \w     58.00 124.00   1.00    1.00    --   95.80 -82.00 -60.00   66
 68  \w     78.00 104.00   1.00    1.00    --   95.80  41.00 -76.05   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0772698000
_diffrn_orient_matrix_UB_12      0.0076525000
_diffrn_orient_matrix_UB_13      0.1436538000
_diffrn_orient_matrix_UB_21      0.1223926000
_diffrn_orient_matrix_UB_22      0.0102416000
_diffrn_orient_matrix_UB_23      -0.0147312000
_diffrn_orient_matrix_UB_31      -0.0119618000
_diffrn_orient_matrix_UB_32      0.1532883000
_diffrn_orient_matrix_UB_33      -0.0061370000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1046
_diffrn_reflns_av_unetI/netI     0.0480
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            28598
_diffrn_reflns_point_group_measured_fraction_full 0.948
_diffrn_reflns_point_group_measured_fraction_max 0.928
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.550
_diffrn_reflns_theta_min         4.147
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.297
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.33494
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_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    1.455
_exptl_crystal_description       block
_exptl_crystal_F_000             568
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.36
_exptl_crystal_size_min          0.35
_refine_diff_density_max         0.578
_refine_diff_density_min         -0.651
_refine_diff_density_rms         0.078
_refine_ls_abs_structure_details
;
 Flack x determined using 1857 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.037(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     318
_refine_ls_number_reflns         4806
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0436
_refine_ls_R_factor_gt           0.0420
_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^)+(0.0759P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1106
_refine_ls_wR_factor_ref         0.1116
_reflns_Friedel_coverage         0.777
_reflns_Friedel_fraction_full    0.889
_reflns_Friedel_fraction_max     0.862
_reflns_number_gt                4590
_reflns_number_total             4806
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b01955_si_002.cif
_cod_data_source_block           exp_622
_cod_original_cell_volume        1265.38(4)
_cod_database_code               4033607
_shelx_shelxl_version_number     2016/6
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Riding coordinates:
 N2(H2)
2.b Ternary CH refined with riding coordinates:
 C1(H1)
2.c Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B)
2.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C14(H14), C16(H16), C17(H17), C18(H18),
 C20(H20), C21(H21), C23(H23), C24(H24)
2.e Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C26(H26A,H26B,H26C)
;
_shelx_res_checksum              15201
_shelx_hkl_checksum              47726
_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 5.398
_oxdiff_exptl_absorpt_empirical_full_min 0.248