Catalytic Enantioselective Synthesis of 3,4-Unsubstituted Thiochromenes through Sulfa-Michael/Julia-Kocienski Olefination Cascade Reaction.
Simlandy, Amit Kumar; Mukherjee, Santanu; The Journal of organic chemistry 82 (2017) 4851–4858; doi:10.1021/acs.joc.7b00579

data_4032538
_publ_section_title
;
 Catalytic Enantioselective Synthesis of 3,4-Unsubstituted Thiochromenes
 through Sulfa-Michael/Julia-Kocienski Olefination Cascade Reaction.
;
_journal_issue                   9
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              4851
_journal_page_last               4858
_journal_paper_doi               10.1021/acs.joc.7b00579
_journal_volume                  82
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C15 H11 Br S'
_chemical_formula_sum            'C15 H11 Br S'
_chemical_formula_weight         303.21
_chemical_name_systematic        AKSIII_099
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2016-06-07
_audit_creation_method
;
  Olex2 1.2
  (compiled 2012.05.09 svn.r2324, GUI svn.r4230)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   10.9526(7)
_cell_length_b                   11.6626(10)
_cell_length_c                   29.560(2)
_cell_measurement_reflns_used    2630
_cell_measurement_temperature    102(3)
_cell_measurement_theta_max      25.0710
_cell_measurement_theta_min      3.2670
_cell_volume                     3775.9(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
olex2.solve (L.J. Bourhis, O.V. Dolomanov, R.J. Gildea, J.A.K. Howard,
H. Puschmann, in preparation, 2011)
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      102(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0419
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.898
_diffrn_measured_fraction_theta_max 0.997
_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    -84.00 -44.00   1.00   15.00    --  -11.54 179.00 -60.00   40
  2  \w    -62.00 -27.00   1.00   15.00    --  -11.54 -57.00 -30.00   35
  3  \w    -37.00  41.00   1.00   15.00    --   15.83 -77.00 150.00   78
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Nova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0395987000
_diffrn_orient_matrix_UB_12      -0.0480969000
_diffrn_orient_matrix_UB_13      -0.0006827000
_diffrn_orient_matrix_UB_21      0.0191282000
_diffrn_orient_matrix_UB_22      -0.0159743000
_diffrn_orient_matrix_UB_23      0.0220423000
_diffrn_orient_matrix_UB_31      -0.0475239000
_diffrn_orient_matrix_UB_32      0.0336545000
_diffrn_orient_matrix_UB_33      0.0094493000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0506
_diffrn_reflns_av_unetI/netI     0.1039
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            11268
_diffrn_reflns_point_group_measured_fraction_full 0.938
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         2.551
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Mova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.404
_exptl_absorpt_correction_T_max  0.857
_exptl_absorpt_correction_T_min  0.704
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
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 light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.600
_exptl_crystal_description       block
_exptl_crystal_F_000             1824
_exptl_crystal_size_max          0.171
_exptl_crystal_size_mid          0.124
_exptl_crystal_size_min          0.047
_refine_diff_density_max         0.493
_refine_diff_density_min         -0.462
_refine_diff_density_rms         0.105
_refine_ls_abs_structure_details
;
 Flack x determined using 1380 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.002(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.998
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     460
_refine_ls_number_reflns         6221
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.998
_refine_ls_R_factor_all          0.0842
_refine_ls_R_factor_gt           0.0557
_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^)+(0.0143P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0797
_refine_ls_wR_factor_ref         0.0892
_reflns_Friedel_coverage         0.666
_reflns_Friedel_fraction_full    0.860
_reflns_Friedel_fraction_max     0.860
_reflns_number_gt                4720
_reflns_number_total             6221
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b00579_si_002.cif
_cod_data_source_block           3ai
_cod_database_code               4032538
_chemical_oxdiff_formula         'C10 H8 N1 O2 S1 Br1'
_reflns_odcompleteness_completeness 86.67
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Ternary CH refined with riding coordinates:
 C12(H12), C2BA(H2BA), C19(H19)
2.b Aromatic/amide H refined with riding coordinates:
 C4AA(H4AA), C1AA(H1AA), C0AA(H0AA), C7AA(H7AA), C17(H17), C4BA(H4BA),
 C6BA(H6BA), C8BA(H8BA), C11(H11), C6(H6), C6AA(H6AA), C0BA(H0BA), C2CA(H2CA),
 C16(H16), C3BA(H3BA), C2(H2), C1BA(H1BA), C15(H15), C20(H20), C1CA(H1CA),
 C0CA(H0CA), C4(H4), C7(H7), C8(H8), C13(H13), C1(H1), C3(H3), C3CA(H3CA),
 C5(H5), C4CA(H4CA)
;
_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 1.642
_oxdiff_exptl_absorpt_empirical_full_min 0.845
_shelx_hkl_checksum              3954
_shelx_res_checksum              19013
_shelx_shelxl_version_number     2014/7