Asymmetric tandem conjugate addition−protonation to forge chiral secondary C−O bond for quaternary carbon stereocenters at the nonadjacent β-position
Hong, San-Ni; Liu, Yang; Lee, Richmond; Jiang, Zhiyong; Chem. Commun.  (2017) –; doi:10.1039/C7CC03700G

data_7120269
_publ_section_title
;
 Asymmetric tandem conjugate addition&#x2212;protonation to forge chiral
 secondary C&#x2212;O bond for quaternary carbon stereocenters at the
 nonadjacent \b-position
;
_journal_name_full               'Chem. Commun.'
_journal_paper_doi               10.1039/C7CC03700G
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C17 H17 N O3 S'
_chemical_formula_sum            'C17 H17 N O3 S'
_chemical_formula_weight         315.37
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_symmetry_space_group_name_Hall  'C 2y'
_symmetry_space_group_name_H-M   'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2016-11-11
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_audit_update_record
;
2017-02-09 deposited with the CCDC.
2017-06-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.427(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.1001(5)
_cell_length_b                   6.5764(3)
_cell_length_c                   29.8228(17)
_cell_measurement_reflns_used    2060
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      69.6010
_cell_measurement_theta_min      4.4670
_cell_volume                     1578.66(15)
_computing_cell_refinement       'CrysAlisPro 1.171.39.7b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.7b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.7b (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_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_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    -82.00 -30.00   0.50    7.50    --  -33.50 -37.00  87.00  104
  2  \w     30.00  57.00   0.50    7.50    --   36.54  57.00 -60.00   54
  3  \w     85.00 111.00   0.50    7.50    --   36.54 178.00-120.00   52
  4  \w    -13.00  22.00   0.50    7.50    --   36.54   0.00   0.00   70
  5  \w     71.00 107.00   0.50    7.50    --   36.54 178.00 120.00   72
  6  \w     58.00 108.00   0.50    7.50    --   36.54 178.00   0.00  100
  7  \w     65.00  90.00   0.50    7.50    --   36.54  57.00  30.00   50
  8  \w     12.00  37.00   0.50    7.50    --   36.54  77.00   0.00   50
  9  \w      5.00  32.00   0.50    7.50    --   36.54 -99.00  30.00   54
 10  \w     40.00 105.00   0.50    7.50    --   36.54   0.00   0.00  130
 11  \w     60.00  87.00   0.50    7.50    --   36.54  57.00 -60.00   54
 12  \w     57.00  82.00   0.50    7.50    --   36.54 178.00 -90.00   50
 13  \w     62.00 110.00   0.50    7.50    --   36.54 178.00 150.00   96
 14  \w     -1.00  79.00   0.50    7.50    --   36.54  19.00 -60.00  160
 15  \w     -3.00  50.00   0.50    7.50    --   36.54 -99.00-180.00  106
 16  \w     32.00  59.00   0.50    7.50    --   36.54  57.00  60.00   54
 17  \w     43.00  73.00   0.50    7.50    --   36.54 -99.00  30.00   60
 18  \w     65.00  91.00   0.50    7.50    --   36.54  77.00   0.00   52
 19  \w     20.00  63.00   0.50    7.50    --   36.54  57.00  30.00   86
 20  \w     59.00 110.00   0.50    7.50    --   36.54 178.00 -60.00  102
 21  \w      9.00 105.00   0.50    7.50    --   36.54  77.00  90.00  192
 22  \w     62.00  98.00   0.50    7.50    --   36.54  57.00   0.00   72
 23  \w     79.00 110.00   0.50   20.00    --  108.00  77.00 -60.00   62
 24  \w     42.00  85.00   0.50   20.00    --  108.00 -30.00 -30.00   86
 25  \w     81.00 108.00   0.50   20.00    --  108.00  77.00  30.00   54
 26  \w     67.00 104.00   0.50   20.00    --  108.00 -94.00 -90.00   74
 27  \w     83.00 108.00   0.50   20.00    --  108.00  30.00  30.00   50
 28  \w     89.00 169.00   0.50   20.00    --  108.00  61.00 -60.00  160
 29  \w     89.00 117.00   0.50   20.00    --  108.00  61.00  30.00   56
 30  \w     82.00 109.00   0.50   20.00    --  108.00  30.00   0.00   54
 31  \w     37.00  93.00   0.50   20.00    --  108.00-111.00  90.00  112
 32  \w     87.00 133.00   0.50   20.00    --  108.00  65.00 -73.93   92
 33  \w     88.00 114.00   0.50   20.00    --  108.00  61.00 -30.00   52
 34  \w     46.00  98.00   0.50   20.00    --  108.00 -45.00  30.00  104
 35  \w     88.00 155.00   0.50   20.00    --  108.00  61.00 120.00  134
 36  \w    119.00 177.00   0.50   20.00    --  108.00  77.00 -30.00  116
 37  \w    118.00 178.00   0.50   20.00    --  108.00  30.00-120.00  120
 38  \w     63.00  89.00   0.50   20.00    --  108.00  15.00 -30.00   52
 39  \w    125.00 176.00   0.50   20.00    --  108.00  77.00   0.00  102
 40  \w     59.00  86.00   0.50   20.00    --  108.00 -45.00 -90.00   54
 41  \w     82.00 127.00   0.50   20.00    --  108.00  30.00  60.00   90
 42  \w     79.00 105.00   0.50   20.00    --  108.00  77.00   0.00   52
 43  \w     79.00 106.00   0.50   20.00    --  108.00  77.00 -30.00   54
 44  \w     88.00 115.00   0.50   20.00    --  108.00  61.00   0.00   54
 45  \w     79.00 106.00   0.50   20.00    --  108.00  77.00 -90.00   54
 46  \w     38.00 109.00   0.50   20.00    --  108.00 -94.00-180.00  142
 47  \w     92.00 117.00   0.50   20.00    --  108.00  30.00-120.00   50
 48  \w     79.00 106.00   0.50   20.00    --  108.00  78.00  13.35   54
 49  \w     84.00 110.00   0.50   20.00    --  108.00  30.00 -60.00   52
 50  \w     80.00 113.00   0.50   20.00    --  108.00  27.00 -46.85   66
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1686235000
_diffrn_orient_matrix_UB_12      -0.1075236000
_diffrn_orient_matrix_UB_13      -0.0007159000
_diffrn_orient_matrix_UB_21      0.0360554000
_diffrn_orient_matrix_UB_22      0.0281730000
_diffrn_orient_matrix_UB_23      0.0514512000
_diffrn_orient_matrix_UB_31      -0.0830791000
_diffrn_orient_matrix_UB_32      -0.2062326000
_diffrn_orient_matrix_UB_33      0.0073664000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0375
_diffrn_reflns_av_unetI/netI     0.0425
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            6505
_diffrn_reflns_point_group_measured_fraction_full 0.951
_diffrn_reflns_point_group_measured_fraction_max 0.951
_diffrn_reflns_theta_full        66.960
_diffrn_reflns_theta_max         66.960
_diffrn_reflns_theta_min         4.476
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.924
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76663
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.7b (Rigaku Oxford Diffraction, 2015)
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    1.327
_exptl_crystal_description       plate
_exptl_crystal_F_000             664
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.558
_refine_diff_density_min         -0.196
_refine_diff_density_rms         0.049
_refine_ls_abs_structure_details
;
 Flack x determined using 695 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   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     214
_refine_ls_number_reflns         2683
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0761
_refine_ls_R_factor_gt           0.0623
_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^)+(0.0923P)^2^+0.6573P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1611
_refine_ls_wR_factor_ref         0.1722
_reflns_Friedel_coverage         0.741
_reflns_Friedel_fraction_full    0.893
_reflns_Friedel_fraction_max     0.893
_reflns_number_gt                2149
_reflns_number_total             2683
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7cc03700g2.cif
_cod_data_source_block           lyaa
_cod_database_code               7120269
_chemical_oxdiff_formula         C20H20N4O2S1
_reflns_odcompleteness_completeness 99.87
_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. Uiso/Uaniso restraints and constraints
Uanis(C17) = Uanis(C17A)
Uanis(C16) = Uanis(C16A)
Uanis(C13) = Uanis(C13A)
Uanis(C14) = Uanis(C14A)
3. Others
 Sof(C13A)=Sof(H13A)=Sof(C14A)=Sof(H14A)=Sof(H15a)=Sof(C16A)=Sof(H16A)=
 Sof(C17A)=Sof(H17A)=1-FVAR(1)
 Sof(C13)=Sof(H13)=Sof(C14)=Sof(H14)=Sof(H15)=Sof(C16)=Sof(H16)=Sof(C17)=
 Sof(H17)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3)
4.b Secondary CH2 refined with riding coordinates:
 C4(H4a,H4b)
4.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C9(H9), C10(H10), C13(H13), C13A(H13A), C14(H14), C14A(H14A),
 C15(H15), C15(H15a), C16(H16), C16A(H16A), C17(H17), C17A(H17A)
4.d Idealised Me refined as rotating group:
 C11(H11a,H11b,H11c)
4.e Idealised tetrahedral OH refined as rotating group:
 O3(H3a)
;
_shelx_res_checksum              44961
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-11-09
_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 1.339
_oxdiff_exptl_absorpt_empirical_full_min 0.802