Chiral Bifunctional Thioureas and Squaramides and Their Copolymers as Recoverable Organocatalysts. Stereoselective Synthesis of 2-Substituted 4-Amino-3-nitrobenzopyrans and 3-Functionalized 3,4-Diamino-4 H-Chromenes.
Andrés, José M; Maestro, Alicia; Valle, María; Pedrosa, Rafael; The Journal of organic chemistry 83 (2018) 5546–5557; doi:10.1021/acs.joc.8b00567

data_4034796
_publ_section_title
;
 Chiral Bifunctional Thioureas and Squaramides and Their Copolymers as
 Recoverable Organocatalysts. Stereoselective Synthesis of 2-Substituted
 4-Amino-3-nitrobenzopyrans and 3-Functionalized 3,4-Diamino-4
 H-Chromenes.
;
_journal_issue                   10
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              5546
_journal_page_last               5557
_journal_paper_doi               10.1021/acs.joc.8b00567
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C20 H22 N2 O5 S'
_chemical_formula_sum            'C20 H22 N2 O5 S'
_chemical_formula_weight         402.45
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-05-25
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                66.686(3)
_cell_angle_beta                 83.345(2)
_cell_angle_gamma                75.053(3)
_cell_formula_units_Z            2
_cell_length_a                   9.7904(3)
_cell_length_b                   9.9854(3)
_cell_length_c                   11.9075(4)
_cell_measurement_reflns_used    17213
_cell_measurement_temperature    293
_cell_measurement_theta_max      74.9150
_cell_measurement_theta_min      4.0310
_cell_volume                     1032.75(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      293
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4757
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.987
_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      3.00  35.00   1.00    1.00    --   38.00  86.00 126.52   32
  2  \w   -114.00 -13.00   1.00    1.00    --  -40.81 -57.00  30.00  101
  3  \w    -65.00  34.00   1.00    1.00    --  -40.81  37.00  60.00   99
  4  \w   -121.00   0.00   1.00    1.00    --  -40.81 -19.00  60.00  121
  5  \w   -115.00 -16.00   1.00    1.00    --  -40.81 -37.00-120.00   99
  6  \w     56.00 129.00   1.00    1.00    --   40.81 179.00-180.00   73
  7  \w    -34.00  65.00   1.00    1.00    --   40.81 -37.00  60.00   99
  8  \w     55.00 128.00   1.00    1.00    --   40.81-179.00   0.00   73
  9  \w     11.00  38.00   1.00    1.00    --   46.00  84.00 -52.31   27
 10  \w     16.00  45.00   1.00    1.00    --   50.00  82.00-120.71   29
 11  \w     21.00  47.00   1.00    1.00    --   54.00  79.00-168.34   26
 12  \w     20.00  46.00   1.00    1.00    --   54.00  81.00   9.32   26
 13  \w     20.00  46.00   1.00    1.00    --   54.00  81.00  87.31   26
 14  \w     25.00 134.00   1.00    1.00    --   58.00  77.00  -4.39  109
 15  \w     30.00 138.00   1.00    1.00    --   62.00  76.00  86.60  108
 16  \w     33.00 142.00   1.00    1.00    --   66.00  77.00-164.00  109
 17  \w     34.00 142.00   1.00    1.00    --   66.00  76.00 -35.54  108
 18  \w     34.00 142.00   1.00    1.00    --   66.00  76.00 127.01  108
 19  \w     34.00 142.00   1.00    1.00    --   66.00  76.00  39.03  108
 20  \w     37.00 146.00   1.00    1.00    --   70.00  77.00-142.13  109
 21  \w     41.00 150.00   1.00    1.00    --   74.00  77.00-130.88  109
 22  \w     41.00 150.00   1.00    1.00    --   74.00  77.00 -90.56  109
 23  \w     37.00 121.00   1.00    1.00    --  110.01-125.00-120.00   84
 24  \w     77.00 178.00   1.00    1.00    --  110.01  77.00  60.00  101
 25  \w     77.00 178.00   1.00    1.00    --  110.01  77.00 -90.00  101
 26  \w     81.00 178.00   1.00    1.00    --  110.01  61.00 120.00   97
 27  \w     81.00 178.00   1.00    1.00    --  110.01  61.00   0.00   97
 28  \w     81.00 178.00   1.00    1.00    --  110.01  61.00  90.00   97
 29  \w     77.00 178.00   1.00    1.00    --  110.01  77.00 120.00  101
 30  \w     81.00 178.00   1.00    1.00    --  110.01  61.00  30.00   97
 31  \w     81.00 178.00   1.00    1.00    --  110.01  61.00 -30.00   97
 32  \w     27.00 109.00   1.00    1.00    --  110.01 -94.00 -90.00   82
 33  \w     77.00 178.00   1.00    1.00    --  110.01  77.00-150.00  101
 34  \w     81.00 178.00   1.00    1.00    --  110.01  61.00 150.00   97
 35  \w     81.00 178.00   1.00    1.00    --  110.01  61.00  60.00   97
 36  \w     77.00 178.00   1.00    1.00    --  110.01  77.00  90.00  101
 37  \w     77.00 178.00   1.00    1.00    --  110.01  77.00   0.00  101
 38  \w     27.00 109.00   1.00    1.00    --  110.01 -94.00  90.00   82
 39  \w     77.00 178.00   1.00    1.00    --  110.01  77.00 -30.00  101
 40  \w     37.00 136.00   1.00    1.00    --  110.01 -45.00  30.00   99
 41  \w     81.00 178.00   1.00    1.00    --  110.01  61.00-180.00   97
 42  \w     77.00 178.00   1.00    1.00    --  110.01  77.00-180.00  101
 43  \w     77.00 178.00   1.00    1.00    --  110.01  77.00-120.00  101
 44  \w     77.00 178.00   1.00    1.00    --  110.01  77.00  30.00  101
 45  \w     81.00 178.00   1.00    1.00    --  110.01  61.00 -60.00   97
 46  \w     77.00 178.00   1.00    1.00    --  110.01  77.00 -60.00  101
 47  \w     77.00 178.00   1.00    1.00    --  110.01  77.00 150.00  101
 48  \w     27.00 109.00   1.00    1.00    --  110.01 -94.00   0.00   82
 49  \w   -114.00 -13.00   1.00    1.00    --  -40.81 -57.00 -60.00  101
 50  \w     15.00 120.00   1.00    1.00    --   46.00  71.00  14.93  105
 51  \w     16.00  45.00   1.00    1.00    --   50.00  82.00 -89.18   29
 52  \w     16.00  46.00   1.00    1.00    --   50.00  81.00  46.04   30
 53  \w     20.00  46.00   1.00    1.00    --   54.00  81.00-112.17   26
 54  \w     21.00  47.00   1.00    1.00    --   54.00  79.00 153.66   26
 55  \w     20.00  46.00   1.00    1.00    --   54.00  81.00 -30.46   26
 56  \w     25.00 134.00   1.00    1.00    --   58.00  77.00 157.04  109
 57  \w     29.00 138.00   1.00    1.00    --   62.00  77.00 -46.41  109
 58  \w     29.00 138.00   1.00    1.00    --   62.00  77.00-171.01  109
 59  \w     29.00 138.00   1.00    1.00    --   62.00  77.00 119.80  109
 60  \w     30.00 138.00   1.00    1.00    --   62.00  76.00  68.57  108
 61  \w     30.00 137.00   1.00    1.00    --   62.00  75.00 -81.07  107
 62  \w     38.00 146.00   1.00    1.00    --   70.00  76.00-103.84  108
 63  \w     38.00 146.00   1.00    1.00    --   70.00  76.00 -70.78  108
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0742137000
_diffrn_orient_matrix_UB_12      -0.1329604000
_diffrn_orient_matrix_UB_13      -0.0368769000
_diffrn_orient_matrix_UB_21      0.1403128000
_diffrn_orient_matrix_UB_22      -0.0049829000
_diffrn_orient_matrix_UB_23      0.0499088000
_diffrn_orient_matrix_UB_31      -0.0365496000
_diffrn_orient_matrix_UB_32      -0.1101498000
_diffrn_orient_matrix_UB_33      0.1264974000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0438
_diffrn_reflns_av_unetI/netI     0.0217
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            36614
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.001
_diffrn_reflns_theta_min         4.043
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.675
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.339
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
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    1.294
_exptl_crystal_description       block
_exptl_crystal_F_000             424
_exptl_crystal_size_max          0.481
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.205
_refine_diff_density_min         -0.409
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     264
_refine_ls_number_reflns         4211
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0441
_refine_ls_R_factor_gt           0.0375
_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^)+(0.0540P)^2^+0.2550P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0959
_refine_ls_wR_factor_ref         0.1020
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3671
_reflns_number_total             4211
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b00567_si_001.cif
_cod_data_source_block           2
_cod_database_code               4034796
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C14 H15 N2 O4 S'
_chemical_oxdiff_usercomment     colorless
_reflns_odcompleteness_completeness 100.00
_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 N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C7(H7)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C11(H11), C12(H12), C13(H13),
 C14(H14), C15(H15)
2.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              12472
_shelx_hkl_checksum              49376
_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 1.339
_oxdiff_exptl_absorpt_empirical_full_min 0.691