Asymmetric [4 + 2] cycloaddition synthesis of 4H-chromene derivatives facilitated by group-assisted-purification (GAP) chemistry
Rouh, Hossein; Tang, Yao; Zhang, Sai; Ali, Ahmed I. M.; Surowiec, Kazimierz; Unruh, Daniel; Li, Guigen; RSC Advances 11 (2021) 39790–39796; doi:10.1039/D1RA08323F

data_7244054
_publ_section_title
;
 Asymmetric [4 + 2] cycloaddition synthesis of 4H-chromene derivatives
 facilitated by group-assisted-purification (GAP) chemistry
;
_journal_issue                   63
_journal_name_full               'RSC Advances'
_journal_page_first              39790
_journal_page_last               39796
_journal_paper_doi               10.1039/D1RA08323F
_journal_volume                  11
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C30 H40 N3 O4 P'
_chemical_formula_sum            'C30 H40 N3 O4 P'
_chemical_formula_weight         537.62
_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             2021-02-08
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.03.28 svn.rd84adfe8 for Rigaku Oxford Diffraction, GUI svn.r6032)
;
_audit_update_record
;
2021-10-08 deposited with the CCDC.	2021-12-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.46724(4)
_cell_length_b                   21.50060(15)
_cell_length_c                   23.19943(16)
_cell_measurement_reflns_used    26149
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      77.4720
_cell_measurement_theta_min      2.7520
_cell_volume                     2727.07(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -41.00  25.00   0.50    0.82    --  -48.34  38.00  84.00  132
  2  \w    -49.00 -14.00   0.50    3.29    --  -86.25  45.00 -60.00   70
  3  \w    -24.00  27.00   0.50    0.82    --  -48.34  19.00-120.00  102
  4  \w    -81.00 -13.00   0.50    3.29    --  -86.25 107.00 -61.00  136
  5  \w   -121.00 -36.00   0.50    0.82    --  -48.34 -38.00 -71.00  170
  6  \w   -120.00 -73.00   0.50    0.82    --  -48.34-125.00-150.00   94
  7  \w   -120.00 -26.00   0.50    0.82    --  -48.34 -77.00-180.00  188
  8  \w   -120.00 -73.00   0.50    0.82    --  -48.34-125.00   0.00   94
  9  \w   -120.00 -33.00   0.50    0.82    --  -48.34 -57.00-120.00  174
 10  \w     34.00 120.00   0.50    0.82    --   48.34  57.00  60.00  172
 11  \w    105.00 178.00   0.50    3.29    --  107.75 107.00 -61.00  146
 12  \w     95.00 178.00   0.50    3.29    --  107.75  38.00  84.00  166
 13  \w     95.00 178.00   0.50    3.29    --  107.75 125.00 -30.00  166
 14  \w     95.00 178.00   0.50    3.29    --  107.75  45.00-150.00  166
 15  \w     35.00 107.00   0.50    3.29    --  107.75 -77.00 -60.00  144
 16  \w     35.00 106.00   0.50    3.29    --  107.75 -90.00  95.00  142
 17  \w     35.00  73.00   0.50    3.29    --  107.75 -61.00 120.00   76
 18  \w     35.00  73.00   0.50    3.29    --  107.75 -61.00 150.00   76
 19  \w     35.00  73.00   0.50    3.29    --  107.75 -61.00  90.00   76
 20  \w     35.00 112.00   0.50    3.29    --  107.75-125.00  60.00  154
 21  \w     35.00  73.00   0.50    3.29    --  107.75 -61.00 -60.00   76
 22  \w     95.00 178.00   0.50    3.29    --  107.75  30.00 150.00  166
 23  \w   -159.00 -79.00   0.50    3.29    --  -86.25 -90.00  95.00  160
 24  \w   -159.00-107.00   0.50    3.29    --  -86.25 -77.00 -90.00  104
 25  \w   -159.00 -73.00   0.50    3.29    --  -86.25 -38.00 -71.00  172
 26  \w   -159.00 -63.00   0.50    3.29    --  -86.25 -77.00-150.00  192
 27  \w   -158.00 -73.00   0.50    3.29    --  -86.25 -45.00   0.00  170
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1351228000
_diffrn_orient_matrix_UB_12      -0.0247309000
_diffrn_orient_matrix_UB_13      0.0535864000
_diffrn_orient_matrix_UB_21      -0.0148563000
_diffrn_orient_matrix_UB_22      -0.0649621000
_diffrn_orient_matrix_UB_23      -0.0278055000
_diffrn_orient_matrix_UB_31      0.2467722000
_diffrn_orient_matrix_UB_32      -0.0174302000
_diffrn_orient_matrix_UB_33      0.0276607000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0458
_diffrn_reflns_av_unetI/netI     0.0270
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            32739
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.233
_diffrn_reflns_theta_min         2.802
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.223
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.580
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.309
_exptl_crystal_description       needle
_exptl_crystal_F_000             1152
_exptl_crystal_recrystallization_method 'Slow evaporation from methanol'
_exptl_crystal_size_max          0.241
_exptl_crystal_size_mid          0.071
_exptl_crystal_size_min          0.057
_refine_diff_density_max         0.253
_refine_diff_density_min         -0.286
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 1992 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.004(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     351
_refine_ls_number_reflns         5001
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0272
_refine_ls_R_factor_gt           0.0260
_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^)+(0.0374P)^2^+0.5086P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0670
_refine_ls_wR_factor_ref         0.0676
_reflns_Friedel_coverage         0.720
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                4822
_reflns_number_total             5001
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ra08323f2.cif
_cod_data_source_block           1
_cod_database_code               7244054
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C120  H160  N12  O16  P4  '
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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 Ternary CH refined with riding coordinates:
 C1(H1A), C19(H19), C24(H24), C25(H25), C28(H28)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C14(H14), C15(H15), C16(H16), C17(H17),
 C18(H18)
2.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C29(H29A,H29B,
 H29C), C30(H30A,H30B,H30C)
;
_shelx_res_checksum              6580
_olex2_exptl_crystal_mounting_method 'MiTeGen 50 micron MicroLoop'
_olex2_submission_original_sample_id Li21_03
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_diffrn_reflns_filtered   1571
_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 2.328
_oxdiff_exptl_absorpt_empirical_full_min 0.567