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_7157088
_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         'C33 H31 N O4 S'
_chemical_formula_sum            'C33 H31 N O4 S'
_chemical_formula_weight         537.65
_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             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                 96.115(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.2545(7)
_cell_length_b                   9.0908(5)
_cell_length_c                   32.563(3)
_cell_measurement_reflns_used    3359
_cell_measurement_temperature    150
_cell_measurement_theta_max      29.1190
_cell_measurement_theta_min      2.3170
_cell_volume                     2724.0(4)
_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 0.965
_diffrn_measured_fraction_theta_max 0.965
_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    -94.00  70.00   0.50    8.00    --  -20.00   0.00  36.00  328
  2  \w   -110.00   3.00   0.50    8.00    --  -20.00 -72.00  36.00  226
;
_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      -0.0328254000
_diffrn_orient_matrix_UB_12      0.0693787000
_diffrn_orient_matrix_UB_13      -0.0045615000
_diffrn_orient_matrix_UB_21      0.0032342000
_diffrn_orient_matrix_UB_22      0.0156700000
_diffrn_orient_matrix_UB_23      0.0214372000
_diffrn_orient_matrix_UB_31      0.0696273000
_diffrn_orient_matrix_UB_32      0.0320018000
_diffrn_orient_matrix_UB_33      -0.0005753000
_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  0.0962
_diffrn_reflns_av_unetI/netI     0.1030
_diffrn_reflns_Laue_measured_fraction_full 0.965
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            13976
_diffrn_reflns_point_group_measured_fraction_full 0.965
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        24.996
_diffrn_reflns_theta_max         24.996
_diffrn_reflns_theta_min         2.327
_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    0.159
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64544
_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    1.311
_exptl_crystal_description       block
_exptl_crystal_F_000             1136
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.400
_refine_diff_density_min         -0.731
_refine_diff_density_rms         0.100
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     355
_refine_ls_number_reflns         4633
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.1096
_refine_ls_R_factor_gt           0.0709
_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^)+(0.0636P)^2^+1.2446P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1451
_refine_ls_wR_factor_ref         0.1715
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3241
_reflns_number_total             4633
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob02030f2.cif
_cod_data_source_block           sjg-djf-4-32_mo
_cod_depositor_comments
'Adding full bibliography for 7157086--7157091.cif.'
_cod_original_cell_volume        2724.0(3)
_cod_database_code               7157088
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.967
_reflns_odcompleteness_completeness 82.01
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     31.08
_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:
 C16(H16)
2.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C27(H27), C3(H3), C9(H9), C8(H8), C6(H6), C32(H32), C7(H7), C21(H21),
 C11(H11), C29(H29), C20(H20), C31(H31), C10(H10), C23(H23), C24(H24), C30(H30)
2.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C17(H17A,H17B,H17C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              82556
_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 1.297
_oxdiff_exptl_absorpt_empirical_full_min 0.748