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_7157086
_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_formula_moiety         'C31 H27 N O4 S'
_chemical_formula_sum            'C31 H27 N O4 S'
_chemical_formula_weight         509.59
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-11-27
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-12-14 deposited with the CCDC.    2019-09-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.449(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.6522(10)
_cell_length_b                   13.6042(7)
_cell_length_c                   12.4636(8)
_cell_measurement_reflns_used    4882
_cell_measurement_temperature    150
_cell_measurement_theta_max      30.6720
_cell_measurement_theta_min      2.2650
_cell_volume                     2531.8(3)
_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 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   -110.00  53.00   0.50    8.00    --  -20.00   0.00 108.00  326
  2  \w     19.00  44.00   0.50    8.00    --  -20.00  72.00-108.00   50
;
_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      -0.0127904000
_diffrn_orient_matrix_UB_12      -0.0323418000
_diffrn_orient_matrix_UB_13      -0.0466929000
_diffrn_orient_matrix_UB_21      0.0450140000
_diffrn_orient_matrix_UB_22      -0.0161525000
_diffrn_orient_matrix_UB_23      0.0121147000
_diffrn_orient_matrix_UB_31      -0.0083008000
_diffrn_orient_matrix_UB_32      -0.0375470000
_diffrn_orient_matrix_UB_33      0.0350895000
_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  0.0594
_diffrn_reflns_av_unetI/netI     0.0832
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            8847
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         2.025
_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    0.167
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.41085
_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    1.337
_exptl_crystal_description       block
_exptl_crystal_F_000             1072
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.353
_refine_diff_density_min         -0.525
_refine_diff_density_rms         0.107
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     336
_refine_ls_number_reflns         4454
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0830
_refine_ls_R_factor_gt           0.0560
_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^)+(0.1005P)^2^+0.0997P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1417
_refine_ls_wR_factor_ref         0.1878
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3337
_reflns_number_total             4454
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob02030f2.cif
_cod_data_source_block           sjg-sn-10-1480_mo
_cod_depositor_comments
'Adding full bibliography for 7157086--7157091.cif.'
_cod_database_code               7157086
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.995
_shelx_estimated_absorpt_t_min   0.941
_reflns_odcompleteness_completeness 88.16
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.98
_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:
 C30(H30)
2.b Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B)
2.c Aromatic/amide H refined with riding coordinates:
 C28(H28), C12(H12), C22(H22), C11(H11), C21(H21), C25(H25), C10(H10),
 C17(H17), C9(H9), C26(H26), C20(H20), C27(H27), C6(H6), C19(H19), C18(H18),
 C3(H3), C4(H4), C7(H7)
2.d Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C1(H1A,H1B,H1C)
;
_shelx_res_checksum              4111
_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 2.511
_oxdiff_exptl_absorpt_empirical_full_min 0.507