Enantioselective synthesis of trifluoromethyl substituted cyclohexanones via an organocatalytic cascade Michael/aldol reaction.
Yang, Hongzhou; Wang, Qingqing; Luo, Yuan; Ye, Ling; Li, Xinying; Chen, Feng; Zhao, Zhigang; Li, Xuefeng; Organic & biomolecular chemistry 18 (2020) 1607–1611; doi:10.1039/d0ob00004c

data_7157335
_publ_section_title
;
 Enantioselective synthesis of trifluoromethyl substituted cyclohexanones
 via an organocatalytic cascade Michael/aldol reaction.
;
_journal_issue                   8
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              1607
_journal_page_last               1611
_journal_paper_doi               10.1039/d0ob00004c
_journal_volume                  18
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C14 H15 F3 O4 S'
_chemical_formula_sum            'C14 H15 F3 O4 S'
_chemical_formula_weight         336.32
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'I 2y'
_space_group_name_H-M_alt        'I 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-07-20
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-12-23 deposited with the CCDC.	2020-02-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.086(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.4373(11)
_cell_length_b                   5.6433(3)
_cell_length_c                   16.0752(9)
_cell_measurement_reflns_used    4518
_cell_measurement_temperature    157(10)
_cell_measurement_theta_max      72.9890
_cell_measurement_theta_min      4.2520
_cell_volume                     1540.78(16)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      157(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.987
_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    -55.00  33.00   1.00    1.00    --  -36.29  38.00   0.00   88
  2  \w   -104.00 -20.00   1.00    1.00    --  -36.29 -57.00-150.00   84
  3  \w   -104.00 -20.00   1.00    1.00    --  -36.29 -57.00 150.00   84
  4  \w     20.00 104.00   1.00    1.00    --   36.29  57.00  60.00   84
  5  \w      1.00  75.00   1.00    1.00    --   36.29 -99.00  90.00   74
  6  \w     23.00  90.00   1.00    1.00    --   36.29-125.00 -30.00   67
  7  \w     20.00 104.00   1.00    1.00    --   36.29  57.00  90.00   84
  8  \w     20.00 104.00   1.00    1.00    --   36.29  57.00  30.00   84
  9  \w     57.00 151.00   1.00    3.20    --  108.71 178.00 150.00   94
 10  \w     91.00 177.00   1.00    3.20    --  108.71  45.00 -30.00   86
 11  \w     87.00 178.00   1.00    3.20    --  108.71  30.00-120.00   91
 12  \w     42.00 127.00   1.00    3.20    --  108.71 -61.00 150.00   85
 13  \w    100.00 178.00   1.00    3.20    --  108.71 111.00 150.00   78
 14  \w     91.00 176.00   1.00    3.20    --  108.71  61.00 -60.00   85
 15  \w     39.00 109.00   1.00    3.20    --  108.71 -94.00   0.00   70
 16  \w     91.00 177.00   1.00    3.20    --  108.71  45.00 -90.00   86
 17  \w     39.00 109.00   1.00    3.20    --  108.71 -94.00 -90.00   70
 18  \w     42.00 127.00   1.00    3.20    --  108.71 -61.00   0.00   85
 19  \w     39.00 115.00   1.00    3.20    --  108.71-111.00-180.00   76
 20  \w     40.00 126.00   1.00    3.20    --  108.71 -45.00-120.00   86
 21  \w    -53.00  31.00   1.00    1.00    --  -36.29  57.00-150.00   84
 22  \w     10.00 104.00   1.00    1.00    --   36.29  77.00-180.00   94
 23  \w    -31.00  53.00   1.00    1.00    --   36.29 -57.00  60.00   84
 24  \w     10.00 104.00   1.00    1.00    --   36.29  77.00 -30.00   94
 25  \w     17.00 105.00   1.00    1.00    --   36.29  38.00 -30.00   88
 26  \w     87.00 178.00   1.00    3.20    --  108.71  30.00 150.00   91
 27  \w     70.00 178.00   1.00    3.20    --  108.71  15.00  90.00  108
 28  \w     91.00 170.00   1.00    3.20    --  108.71  61.00   0.00   79
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0415865000
_diffrn_orient_matrix_UB_12      -0.0167105000
_diffrn_orient_matrix_UB_13      -0.0952059000
_diffrn_orient_matrix_UB_21      -0.0687117000
_diffrn_orient_matrix_UB_22      0.1496248000
_diffrn_orient_matrix_UB_23      0.0170648000
_diffrn_orient_matrix_UB_31      0.0420756000
_diffrn_orient_matrix_UB_32      0.2277619000
_diffrn_orient_matrix_UB_33      -0.0181673000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0615
_diffrn_reflns_av_unetI/netI     0.0476
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            8038
_diffrn_reflns_point_group_measured_fraction_full 0.919
_diffrn_reflns_point_group_measured_fraction_max 0.891
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.331
_diffrn_reflns_theta_min         4.252
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.323
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55043
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (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    1.450
_exptl_crystal_description       block
_exptl_crystal_F_000             696
_exptl_crystal_recrystallization_method 'Vapour deposition'
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.590
_refine_diff_density_min         -0.513
_refine_diff_density_rms         0.111
_refine_ls_abs_structure_details
;
 Flack x determined using 893 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     201
_refine_ls_number_reflns         2763
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0851
_refine_ls_R_factor_gt           0.0831
_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^)+(0.1890P)^2^+0.2667P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2220
_refine_ls_wR_factor_ref         0.2261
_reflns_Friedel_coverage         0.633
_reflns_Friedel_fraction_full    0.818
_reflns_Friedel_fraction_max     0.773
_reflns_number_gt                2633
_reflns_number_total             2763
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0ob00004c2.cif
_cod_data_source_block           lq-1d-150k
_cod_depositor_comments
'Adding full bibliography for 7157334--7157335.cif.'
_cod_database_code               7157335
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C5(H5), C10(H10)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C6(H6A,H6B), C13(H13A,H13B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C2(H2A), C1(H1)
2.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C)
2.e Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_shelx_res_checksum              35184
_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 2.874
_oxdiff_exptl_absorpt_empirical_full_min 0.313