Asymmetric Intramolecular Rauhut–Currier Reaction and Its Desymmetric Version via Double Thiol/Phase-Transfer Catalysis
Jiang, Ying; Yang, Yang; He, Qing; Du, Wei; Chen, Ying-Chun; The Journal of Organic Chemistry  (2020) –; doi:10.1021/acs.joc.0c01293

data_4038687
_publ_section_title
;
 Asymmetric Intramolecular Rauhut--Currier Reaction and Its Desymmetric
 Version via Double Thiol/Phase-Transfer Catalysis
;
_journal_name_full               'The Journal of Organic Chemistry'
_journal_paper_doi               10.1021/acs.joc.0c01293
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C35 H27 Cl O2'
_chemical_formula_sum            'C35 H27 Cl O2'
_chemical_formula_weight         515.01
_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             2020-01-15
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.290(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.6569(6)
_cell_length_b                   11.1976(7)
_cell_length_c                   17.9855(9)
_cell_measurement_reflns_used    6852
_cell_measurement_temperature    292.8(9)
_cell_measurement_theta_max      68.9420
_cell_measurement_theta_min      4.6540
_cell_volume                     2728.2(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (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_environment      air
_diffrn_ambient_temperature      292.8(9)
_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 0.986
_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   -107.00  -4.00   1.00    4.64    --  -34.98 -23.00-163.56  103
  2  \w    -53.00  33.00   1.00    4.64    --  -34.98  57.00-180.00   86
  3  \w     13.00 106.00   1.00    4.64    --   34.98  38.00 120.00   93
  4  \w     16.00 103.00   1.00    4.64    --   34.98  57.00   0.00   87
  5  \w     -4.00  21.00   1.00    4.64    --   34.98  97.00 148.28   25
  6  \w     28.00  90.00   1.00    4.64    --   34.98-125.00  90.00   62
  7  \w      1.00  34.00   1.00    4.64    --   34.98 -99.00 150.00   33
  8  \w     27.00  59.00   1.00    4.64    --   34.98  38.00 -90.00   32
  9  \w     25.00  73.00   1.00    4.64    --   34.98  77.00 -90.00   48
 10  \w      1.00  38.00   1.00    4.64    --   34.98 -99.00  30.00   37
 11  \w     17.00  42.00   1.00    4.64    --   34.98  57.00 -60.00   25
 12  \w    -36.00  37.00   1.00    4.64    --   34.98 -38.00  60.00   73
 13  \w     46.00  71.00   1.00    4.64    --   34.98  38.00 -60.00   25
 14  \w     69.00 104.00   1.00    4.64    --   34.98  77.00-180.00   35
 15  \w     23.00  49.00   1.00    4.64    --   34.98  57.00 120.00   26
 16  \w     19.00  44.00   1.00    4.64    --   34.98  57.00 -90.00   25
 17  \w     62.00 101.00   1.00    4.64    --   34.98  57.00 -60.00   39
 18  \w     64.00  97.00   1.00    4.64    --   34.98  57.00-120.00   33
 19  \w     44.00  72.00   1.00    4.64    --   34.98 -99.00-180.00   28
 20  \w      1.00  37.00   1.00    4.64    --   34.98 -99.00-180.00   36
 21  \w     -4.00  21.00   1.00    4.64    --   34.98  98.00  -6.07   25
 22  \w     17.00  42.00   1.00    4.64    --   34.98  57.00-120.00   25
 23  \w     28.00  73.00   1.00    4.64    --   34.98  77.00-150.00   45
 24  \w     61.00  97.00   1.00    4.64    --   34.98  57.00 -30.00   36
 25  \w     15.00  67.00   1.00    4.64    --   34.98  77.00 150.00   52
 26  \w     87.00 112.00   1.00   18.59    --  106.90  61.00 -30.00   25
 27  \w     81.00 106.00   1.00   18.59    --  106.90  30.00-150.00   25
 28  \w    123.00 175.00   1.00   18.59    --  106.90  77.00 -90.00   52
 29  \w     83.00 109.00   1.00   18.59    --  106.90  30.00-120.00   26
 30  \w     87.00 115.00   1.00   18.59    --  106.90  61.00 -90.00   28
 31  \w     78.00 103.00   1.00   18.59    --  106.90  77.00 -90.00   25
 32  \w     78.00 103.00   1.00   18.59    --  106.90  77.00-120.00   25
 33  \w     81.00 109.00   1.00   18.59    --  106.90  30.00   0.00   28
 34  \w    110.00 168.00   1.00   18.59    --  106.90  77.00-150.00   58
 35  \w     81.00 108.00   1.00   18.59    --  106.90  30.00 -30.00   27
 36  \w     85.00 111.00   1.00   18.59    --  106.90  30.00 -90.00   26
 37  \w     78.00 104.00   1.00   18.59    --  106.90  77.00-150.00   26
 38  \w    109.00 136.00   1.00   18.59    --  106.90 -77.00 -90.00   27
 39  \w     87.00 113.00   1.00   18.59    --  106.90  45.00 -60.00   26
 40  \w     87.00 113.00   1.00   18.59    --  106.90  61.00-180.00   26
 41  \w     37.00 102.00   1.00   18.59    --  106.90 -94.00 -90.00   65
 42  \w     89.00 115.00   1.00   18.59    --  106.90  61.00-150.00   26
 43  \w     37.00 108.00   1.00   18.59    --  106.90 -94.00-180.00   71
 44  \w     87.00 118.00   1.00   18.59    --  106.90  45.00 -30.00   31
 45  \w    129.00 166.00   1.00   18.59    --  106.90  61.00 -60.00   37
 46  \w     87.00 113.00   1.00   18.59    --  106.90  61.00 -60.00   26
 47  \w     79.00 105.00   1.00   18.59    --  106.90  77.00 150.00   26
 48  \w     47.00  74.00   1.00   18.59    --  106.90 -94.00 -60.00   27
 49  \w     87.00 113.00   1.00   18.59    --  106.90  61.00-120.00   26
 50  \w     78.00 104.00   1.00   18.59    --  106.90  77.00 -60.00   26
 51  \w    113.00 176.00   1.00   18.59    --  106.90  77.00   0.00   63
 52  \w     88.00 114.00   1.00   18.59    --  106.90  45.00-150.00   26
 53  \w     87.00 113.00   1.00   18.59    --  106.90  45.00-120.00   26
 54  \w     78.00 105.00   1.00   18.59    --  106.90  77.00   0.00   27
 55  \w     82.00 107.00   1.00   18.59    --  106.90  30.00 -60.00   25
 56  \w     87.00 113.00   1.00   18.59    --  106.90  45.00 -90.00   26
 57  \w     88.00 114.00   1.00   18.59    --  106.90  45.00   0.00   26
 58  \w    117.00 175.00   1.00   18.59    --  106.90  61.00 -30.00   58
 59  \w     79.00 105.00   1.00   18.59    --  106.90  77.00 -30.00   26
 60  \w    122.00 147.00   1.00   18.59    --  106.90  77.00-120.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1038090000
_diffrn_orient_matrix_UB_12      0.0009065000
_diffrn_orient_matrix_UB_13      -0.0449707000
_diffrn_orient_matrix_UB_21      0.0463177000
_diffrn_orient_matrix_UB_22      0.0142717000
_diffrn_orient_matrix_UB_23      -0.0732562000
_diffrn_orient_matrix_UB_31      0.0041679000
_diffrn_orient_matrix_UB_32      -0.1368460000
_diffrn_orient_matrix_UB_33      -0.0079261000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0321
_diffrn_reflns_av_unetI/netI     0.0277
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            26069
_diffrn_reflns_point_group_measured_fraction_full 0.882
_diffrn_reflns_point_group_measured_fraction_max 0.860
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.717
_diffrn_reflns_theta_min         3.839
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.468
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.40769
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
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    1.254
_exptl_crystal_description       plate
_exptl_crystal_F_000             1080
_exptl_crystal_size_max          0.7
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.450
_refine_diff_density_min         -0.342
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Flack x determined using 2305 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.011(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     649
_refine_ls_number_reflns         9184
_refine_ls_number_restraints     105
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0959
_refine_ls_R_factor_gt           0.0819
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1767P)^2^+0.4228P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2432
_refine_ls_wR_factor_ref         0.2689
_reflns_Friedel_coverage         0.655
_reflns_Friedel_fraction_full    0.751
_reflns_Friedel_fraction_max     0.719
_reflns_number_gt                7170
_reflns_number_total             9184
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c01293_si_003.cif
_cod_data_source_block           15
_cod_original_cell_volume        2728.2(2)
_cod_database_code               4038687
_shelx_shelxl_version_number     2018/1
_reflns_odcompleteness_completeness 99.94
_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
2. Restrained distances
 C013-C023 = C023-C01R = C01R-C022 = C022-C021 = C021-C00V
 1.39 with sigma of 0.0001
 C013-C020 = C020-C01Z = C01Z-C00P = C00P-C01N = C01N-C00V
 1.39 with sigma of 0.0001
 C00Z-C01W = C01W-C01Y = C01Y-C01U = C01U-C024 = C024-C01E
 1.39 with sigma of 0.0001
 C00Z-C01D = C01D-C00Y = C00Y-C01F = C01F-C01X = C01X-C01E
 1.39 with sigma of 0.0001
 C013-C022 = C023-C021 = C01R-C00V
 2.78 with sigma of 0.02
 C013-C00P = C020-C01N = C01Z-C00V
 2.78 with sigma of 0.02
 C00Z-C01U = C01W-C024 = C01Y-C01E
 2.78 with sigma of 0.02
 C00Z-C01F = C01D-C01X = C00Y-C01E
 2.78 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C020 \\sim C013 \\sim C01Z: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
C022 \\sim C01R \\sim C021: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
C023 \\sim C01R \\sim C021: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
C00Z \\sim C01E: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
C01F \\sim C01X: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
C00V \\sim C013: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
C01E \\sim C024: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
C013 \\sim C023: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
Uanis(C023) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C024) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
4.a Ternary CH refined with riding coordinates:
 C009(H009), C00C(H00C), C00D(H00D), C00F(H00F), C00Q(H00Q), C00R(H00R),
 C00S(H00S), C01B(H01B)
4.b Secondary CH2 refined with riding coordinates:
 C00O(H00A,H00B), C00W(H00E,H00G), C010(H01L,H01M), C017(H01N,H01P), C01H(H01A,
 H01E), C01L(H01H,H01J)
4.c Aromatic/amide H refined with riding coordinates:
 C00L(H00L), C00M(H00M), C011(H011), C012(H012), C015(H015), C016(H016),
 C019(H019), C01C(H01C), C01T(H01T), C01I(H01I), C00T(H00T), C01D(H01D),
 C01F(H01F), C01G(H01G), C01J(H01Q), C01K(H01K), C01N(H01R), C01O(H01O),
 C01R(H01S), C022(H022), C021(H021), C023(H023), C01S(H01V), C01U(H01U),
 C01V(H01Z), C00K(H00K), C018(H018), C01P(H01), C01W(H01W), C01X(H01X),
 C01Y(H01Y), C01Z(H0AA), C020(H020), C024(H024)
4.d Fitted hexagon refined as free rotating group:
 C01C(C01T,C01I,C00I,C01A,C00T), C01R(C022,C021,C00V,C013,C023), C01V(C00J,
 C004,C00K,C018,C01P)
;
_olex2_date_sample_data_collection 2020-01-14
_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 2.424
_oxdiff_exptl_absorpt_empirical_full_min 0.567