Asymmetric Synthesis of CF3- and Indole-Containing Thiochromanes via a Squaramide-Catalyzed Michael-Aldol Reaction.
Zhu, Yuanyuan; Dong, Zhenghao; Cheng, Xin; Zhong, Xiaoling; Liu, Xiaolin; Lin, Li; Shen, Zhiqiang; Yang, Peiju; Li, Yuan; Wang, Hailin; Yan, Wenjin; Wang, Kairong; Wang, Rui; Organic letters 18 (2016) 3546–3549; doi:10.1021/acs.orglett.6b01498

data_1555596
_publ_section_title
;
 Asymmetric Synthesis of CF3- and Indole-Containing Thiochromanes via a
 Squaramide-Catalyzed Michael-Aldol Reaction.
;
_journal_issue                   15
_journal_name_full               'Organic letters'
_journal_page_first              3546
_journal_page_last               3549
_journal_paper_doi               10.1021/acs.orglett.6b01498
_journal_volume                  18
_journal_year                    2016
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C31 H27 Cl F3 N O5 S'
_chemical_formula_sum            'C31 H27 Cl F3 N O5 S'
_chemical_formula_weight         618.04
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-03-14
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 89.999(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.4656(3)
_cell_length_b                   10.4575(2)
_cell_length_c                   26.8799(5)
_cell_measurement_reflns_used    5845
_cell_measurement_temperature    290.83(10)
_cell_measurement_theta_max      23.9900
_cell_measurement_theta_min      3.8850
_cell_volume                     2941.84(12)
_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    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      290.83(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.989
_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    -39.00  33.00   1.00    6.00    --   20.59 -57.00 -60.00   72
  2  \w     -8.00  36.00   1.00    6.00    --   20.59  19.00-180.00   44
  3  \w     -8.00  18.00   1.00    6.00    --  -17.15 -99.00-120.00   26
  4  \w    -16.00  53.00   1.00    6.00    --   20.59 -99.00-180.00   69
  5  \w     -6.00  47.00   1.00    6.00    --   20.59  77.00  90.00   53
  6  \w     57.00  83.00   1.00    6.00    --   20.59  77.00  90.00   26
  7  \w      1.00  88.00   1.00    6.00    --   20.59  77.00 -30.00   87
  8  \w      4.00  75.00   1.00    6.00    --   20.59  77.00-120.00   71
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0077795000
_diffrn_orient_matrix_UB_12      0.0053030000
_diffrn_orient_matrix_UB_13      -0.0261295000
_diffrn_orient_matrix_UB_21      0.0646237000
_diffrn_orient_matrix_UB_22      -0.0194849000
_diffrn_orient_matrix_UB_23      0.0023280000
_diffrn_orient_matrix_UB_31      -0.0187874000
_diffrn_orient_matrix_UB_32      -0.0647823000
_diffrn_orient_matrix_UB_33      -0.0028437000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0386
_diffrn_reflns_av_unetI/netI     0.0563
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            23932
_diffrn_reflns_point_group_measured_fraction_full 0.952
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_theta_full        25.500
_diffrn_reflns_theta_max         26.022
_diffrn_reflns_theta_min         3.572
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.261
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84749
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
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    1.395
_exptl_crystal_description       block
_exptl_crystal_F_000             1280
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.183
_refine_diff_density_min         -0.176
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 2897 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     767
_refine_ls_number_reflns         10946
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.016
_refine_ls_R_factor_all          0.0632
_refine_ls_R_factor_gt           0.0451
_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^)+(0.0431P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0921
_refine_ls_wR_factor_ref         0.1043
_reflns_Friedel_coverage         0.808
_reflns_Friedel_fraction_full    0.909
_reflns_Friedel_fraction_max     0.898
_reflns_number_gt                8591
_reflns_number_total             10946
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol6b01498_si_003.cif
_cod_data_source_block           yanwj_0311
_cod_original_cell_volume        2941.85(11)
_cod_database_code               1555596
_chemical_oxdiff_formula         'C H N O Cl S'
_reflns_odcompleteness_completeness 98.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C7(H7), C8(H8), C38(H38), C39(H39)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C11(H11), C13(H13), C14(H14), C16(H16),
 C25(H25), C26(H26), C28(H28), C29(H29), C33(H33), C34(H34), C35(H35), C36(H36),
  C43(H43), C44(H44), C46(H46), C47(H47), C51(H51), C53(H53), C54(H54), C56(H56)
2.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C30(H30A,H30B,
 H30C), C48(H48A,H48B,H48C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C61(H61A,
 H61B,H61C)
2.d Idealised tetrahedral OH refined as rotating group:
 O1(H1), O6(H6)
;
_shelx_res_checksum              57951
_shelx_hkl_checksum              70035
_shelx_shelxl_version_number     2014/7
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.275
_oxdiff_exptl_absorpt_empirical_full_min 0.757