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_7157087
_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         '2(C28 H29 N O5 S)'
_chemical_formula_sum            'C56 H58 N2 O10 S2'
_chemical_formula_weight         983.16
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-31
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-08-01 deposited with the CCDC.    2019-09-18 downloaded from the CCDC.
;
_cell_angle_alpha                69.467(3)
_cell_angle_beta                 72.006(3)
_cell_angle_gamma                89.666(3)
_cell_formula_units_Z            2
_cell_length_a                   10.6050(4)
_cell_length_b                   16.0358(5)
_cell_length_c                   16.1366(5)
_cell_measurement_reflns_used    17099
_cell_measurement_temperature    150
_cell_measurement_theta_max      31.1800
_cell_measurement_theta_min      2.0620
_cell_volume                     2427.91(16)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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 plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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 -36.00  326
  2  \w   -110.00  19.00   0.50    8.00    --  -20.00 -72.00 -36.00  258
  3  \w    -60.00  19.00   0.50    8.00    --  -20.00 -72.00-180.00  158
  4  \w    -44.00  -1.00   0.50    8.00    --  -20.00  72.00 108.00   86
  5  \w    -40.00 -10.00   0.50    8.00    --  -20.00 -72.00 108.00   60
  6  \w    -40.00 -10.00   0.50    8.00    --  -20.00 -72.00-108.00   60
  7  \w    -59.00  70.00   0.50    8.00    --  -20.00  72.00 -36.00  258
  8  \w    -98.00  19.00   0.50    8.00    --  -20.00 -72.00  36.00  234
  9  \w    -59.00   5.00   0.50    8.00    --  -20.00  72.00-108.00  128
 10  \w    -97.00  25.00   0.50    8.00    --  -20.00   0.00  36.00  244
 11  \w    -43.50  -8.00   0.50    8.00    --  -20.00  72.00-180.00   71
 12  \w   -110.00 -33.50   0.50    8.00    --  -20.00   0.00 108.00  153
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0075380000
_diffrn_orient_matrix_UB_12      -0.0429973000
_diffrn_orient_matrix_UB_13      -0.0028344000
_diffrn_orient_matrix_UB_21      -0.0696633000
_diffrn_orient_matrix_UB_22      -0.0074787000
_diffrn_orient_matrix_UB_23      0.0091723000
_diffrn_orient_matrix_UB_31      0.0100968000
_diffrn_orient_matrix_UB_32      0.0188735000
_diffrn_orient_matrix_UB_33      -0.0487445000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0907
_diffrn_reflns_av_unetI/netI     0.0561
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            47191
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         2.065
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.174
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80796
_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    1.345
_exptl_crystal_description       plate
_exptl_crystal_F_000             1040
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.041
_refine_diff_density_max         0.352
_refine_diff_density_min         -0.498
_refine_diff_density_rms         0.108
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     639
_refine_ls_number_reflns         8552
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0811
_refine_ls_R_factor_gt           0.0571
_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^)+(0.0626P)^2^+1.5253P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1296
_refine_ls_wR_factor_ref         0.1489
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6503
_reflns_number_total             8552
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob02030f2.cif
_cod_data_source_block           sjg-djf-4-105-s2_mo
_cod_depositor_comments
'Adding full bibliography for 7157086--7157091.cif.'
_cod_original_cell_volume        2427.91(15)
_cod_database_code               7157087
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.993
_shelx_estimated_absorpt_t_min   0.966
_reflns_odcompleteness_completeness 91.76
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     31.12
_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:
 C26(H26), C55(H55)
2.b Secondary CH2 refined with riding coordinates:
 C53(H53A,H53B), C25(H25A,H25B), C24(H24A,H24B), C54(H54A,H54B)
2.c Aromatic/amide H refined with riding coordinates:
 C38(H38), C35(H35), C41(H41), C47(H47), C45(H45), C18(H18), C10(H10),
 C31(H31), C19(H19), C9(H9), C37(H37), C48(H48), C44(H44), C15(H15), C16(H16),
 C3(H3), C12(H12), C7(H7), C34(H34), C32(H32), C4(H4), C6(H6), C20(H20),
 C49(H49)
2.d Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C27(H27A,H27B,H27C), C40(H40A,H40B,H40C), C1(H1A,H1B,
 H1C), C23(H23A,H23B,H23C), C28(H28A,H28B,H28C), C52(H52A,H52B,H52C), C56(H56A,
 H56B,H56C)
;
_shelx_res_checksum              13805
_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 1.399
_oxdiff_exptl_absorpt_empirical_full_min 0.680