Expeditious diastereoselective synthesis of medium ring heterocycle-fused chromenes via tandem 8/9-endo-dig and 8-exo-dig hydroalkoxylation-formal-[4 + 2] cycloaddition.
Gharpure, Santosh J.; Nanda, Santosh K.; Fartade, Dipak J.; Organic & biomolecular chemistry 17 (2019) 8806–8810; doi:10.1039/c9ob02030f

data_7157090
_publ_section_title
;
 Expeditious diastereoselective synthesis of medium ring heterocycle-fused
 chromenes via tandem 8/9-endo-dig and 8-exo-dig
 hydroalkoxylation-formal-[4 + 2] cycloaddition.
;
_journal_issue                   39
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              8806
_journal_page_last               8810
_journal_paper_doi               10.1039/c9ob02030f
_journal_volume                  17
_journal_year                    2019
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C33 H31 N O5 S'
_chemical_formula_sum            'C33 H31 N O5 S'
_chemical_formula_weight         553.65
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-28
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-01-29 deposited with the CCDC.    2019-09-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.547(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.1034(2)
_cell_length_b                   9.5264(3)
_cell_length_c                   15.9591(4)
_cell_measurement_reflns_used    13162
_cell_measurement_temperature    150
_cell_measurement_theta_max      31.1260
_cell_measurement_theta_min      2.2860
_cell_volume                     1383.51(6)
_computing_cell_refinement       'CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)'
_computing_data_collection       'CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)'
_computing_data_reduction        'CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)'
_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      150
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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   -110.00  16.00   0.50    8.00    --  -20.00   0.00-108.00  252
  2  \w    -74.50  17.00   0.50    8.00    --  -20.00 -72.00-180.00  183
  3  \w    -18.00  12.50   0.50    8.00    --  -20.00 -72.00  36.00   61
  4  \w   -110.00  70.00   0.50    8.00    --  -20.00   0.00-180.00  360
  5  \w    -49.50   7.00   0.50    8.00    --  -20.00  72.00-180.00  113
  6  \w    -41.00 -10.50   0.50    8.00    --  -20.00 -72.00-108.00   61
  7  \w    -49.00 -19.00   0.50    8.00    --  -20.00 -72.00 108.00   60
;
_diffrn_measurement_device       'AFC12 (Right): Kappa 3 circle'
_diffrn_measurement_device_type  'Rigaku Saturn724+ (2x2 bin mode)'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0168218000
_diffrn_orient_matrix_UB_12      -0.0719254000
_diffrn_orient_matrix_UB_13      0.0060661000
_diffrn_orient_matrix_UB_21      -0.0053311000
_diffrn_orient_matrix_UB_22      -0.0097284000
_diffrn_orient_matrix_UB_23      -0.0440303000
_diffrn_orient_matrix_UB_31      0.0759420000
_diffrn_orient_matrix_UB_32      -0.0166183000
_diffrn_orient_matrix_UB_33      -0.0004814000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0394
_diffrn_reflns_av_unetI/netI     0.0355
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            14363
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        24.986
_diffrn_reflns_theta_max         24.986
_diffrn_reflns_theta_min         2.490
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rotating Anode'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.161
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90771
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.329
_exptl_crystal_description       block
_exptl_crystal_F_000             584
_exptl_crystal_size_max          0.234
_exptl_crystal_size_mid          0.118
_exptl_crystal_size_min          0.055
_refine_diff_density_max         0.230
_refine_diff_density_min         -0.224
_refine_diff_density_rms         0.045
_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   -0.03(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.927
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     364
_refine_ls_number_reflns         4843
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.927
_refine_ls_R_factor_all          0.0352
_refine_ls_R_factor_gt           0.0324
_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^)+(0.0777P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0897
_refine_ls_wR_factor_ref         0.0933
_reflns_Friedel_coverage         0.868
_reflns_Friedel_fraction_full    0.988
_reflns_Friedel_fraction_max     0.988
_reflns_number_gt                4615
_reflns_number_total             4843
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob02030f2.cif
_cod_data_source_block           sjg-sn-10-1569_mo
_cod_depositor_comments
'Adding full bibliography for 7157086--7157091.cif.'
_cod_database_code               7157090
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.963
_reflns_odcompleteness_completeness 92.37
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     31.04
_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:
 C24(H24)
2.b Secondary CH2 refined with riding coordinates:
 C27(H27A,H27B), C25(H25A,H25B)
2.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C15(H15), C11(H11), C7(H7), C12(H12), C6(H6), C9(H9), C4(H4),
 C3(H3), C17(H17), C31(H31), C30(H30), C33(H33), C19(H19), C29(H29), C32(H32),
 C18(H18)
2.d Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C26(H26A,H26B,H26C), C1(H1A,H1B,H1C)
;
_shelx_res_checksum              90023
_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 1.295
_oxdiff_exptl_absorpt_empirical_full_min 0.748