Design, synthesis and application of a new type of bifunctional Le-Phos in highly enantioselective γ-addition reactions of N-centered nucleophiles to allenoates
Qiu, Haile; Chen, Xiaofeng; Zhang, Junliang; Chemical Science 10 (2019) 10510–; doi:10.1039/C9SC04073K

data_1556937
_publ_section_title
;
 Design, synthesis and application of a new type of bifunctional Le-Phos
 in highly enantioselective \g-addition reactions of N-centered
 nucleophiles to allenoates
;
_journal_issue                   45
_journal_name_full               'Chemical Science'
_journal_page_first              10510
_journal_paper_doi               10.1039/C9SC04073K
_journal_volume                  10
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C19 H20 N2 O2 S'
_chemical_formula_sum            'C19 H20 N2 O2 S'
_chemical_formula_weight         340.43
_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     dual
_audit_creation_date             2018-07-10
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-11-23 deposited with the CCDC.	2019-10-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.119(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.2656(3)
_cell_length_b                   9.5413(3)
_cell_length_c                   13.0878(4)
_cell_measurement_reflns_used    6593
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      73.4450
_cell_measurement_theta_min      5.7440
_cell_volume                     893.18(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_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_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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     26.00  88.00   1.00    1.00    --    0.00  57.00  60.00   62
  2  \w     56.00  85.00   1.00    1.00    --    0.00  57.00-120.00   29
  3  \w     35.00  88.00   1.00    1.00    --    0.00  38.00 -60.00   53
  4  \w    -17.00   9.00   1.00    1.00    --    0.00  38.00-150.00   26
  5  \w    -14.00  38.00   1.00    1.00    --    0.00  38.00 120.00   52
  6  \w    -21.00  15.00   1.00    1.00    --    0.00  57.00-120.00   36
  7  \w     47.00  73.00   1.00    1.00    --    0.00  38.00 120.00   26
  8  \w     38.00  87.00   1.00    1.00    --    0.00  38.00   0.00   49
  9  \w     29.00  77.00   1.00    1.00    --    0.00  38.00 150.00   48
 10  \w     21.00  52.00   1.00    1.00    --    0.00  38.00-150.00   31
 11  \w    -22.00  21.00   1.00    1.00    --    0.00  57.00  60.00   43
 12  \w     18.00  52.00   1.00    1.00    --    0.00  57.00-120.00   34
 13  \w    -19.00  29.00   1.00    1.00    --    0.00  38.00   0.00   48
 14  \w     -6.00  26.00   1.00    1.00    --    0.00  38.00 -60.00   32
 15  \w     39.00 115.00   1.00    3.00    --   95.80 -82.00  60.00   76
 16  \w     99.00 124.00   1.00    3.00    --   95.80 -82.00-120.00   25
 17  \w    160.00 185.00   1.00    3.00    --   95.80  66.00 -83.48   25
 18  \w     28.00  75.00   1.00    3.00    --   95.80 -82.00-120.00   47
 19  \w     63.00  94.00   1.00    3.00    --   95.80  82.00  30.00   31
 20  \w     69.00 116.00   1.00    3.00    --   95.80  66.00 -83.48   47
 21  \w    156.00 181.00   1.00    3.00    --   95.80  49.00 100.19   25
 22  \w     63.00  89.00   1.00    3.00    --   95.80  82.00 120.00   26
 23  \w     65.00  91.00   1.00    3.00    --   95.80  77.00  90.00   26
 24  \w     75.00 185.00   1.00    3.00    --   95.80  45.00   0.00  110
 25  \w     75.00 168.00   1.00    3.00    --   95.80  45.00  60.00   93
 26  \w     63.00  89.00   1.00    3.00    --   95.80  82.00-150.00   26
 27  \w    125.00 183.00   1.00    3.00    --   95.80  82.00-150.00   58
 28  \w     75.00 184.00   1.00    3.00    --   95.80  45.00-180.00  109
 29  \w      6.00 125.00   1.00    3.00    --   95.80 -82.00 120.00  119
 30  \w     64.00  97.00   1.00    3.00    --   95.80  82.00 -60.00   33
 31  \w    148.00 185.00   1.00    3.00    --   95.80  82.00  60.00   37
 32  \w     66.00  92.00   1.00    3.00    --   95.80  82.00  60.00   26
 33  \w     71.00 157.00   1.00    3.00    --   95.80  64.00-169.85   86
 34  \w    141.00 167.00   1.00    3.00    --   95.80  45.00 -84.72   26
 35  \w      6.00  35.00   1.00    3.00    --   95.80 -61.00 -60.00   29
 36  \w     76.00 127.00   1.00    3.00    --   95.80  45.00 120.00   51
 37  \w      6.00 128.00   1.00    3.00    --   95.80 -82.00 -30.00  122
 38  \w    155.00 181.00   1.00    3.00    --   95.80  45.00  30.00   26
 39  \w     61.00 102.00   1.00    3.00    --   95.80 -61.00 -60.00   41
 40  \w     65.00  91.00   1.00    3.00    --   95.80  82.00 -90.00   26
 41  \w     75.00 150.00   1.00    3.00    --   95.80  45.00  30.00   75
 42  \w     64.00  89.00   1.00    3.00    --   95.80  82.00   0.00   25
 43  \w     71.00  97.00   1.00    3.00    --   95.80  61.00-180.00   26
 44  \w     15.00 103.00   1.00    3.00    --   95.80 -61.00 120.00   88
 45  \w     65.00  90.00   1.00    3.00    --   95.80  77.00-120.00   25
 46  \w     65.00  91.00   1.00    3.00    --   95.80  77.00 150.00   26
 47  \w    135.00 160.00   1.00    3.00    --   95.80  77.00 150.00   25
 48  \w    131.00 156.00   1.00    3.00    --   95.80  56.00 146.78   25
 49  \w     63.00  88.00   1.00    3.00    --   95.80  82.00-180.00   25
 50  \w     75.00 101.00   1.00    3.00    --   95.80  45.00-120.00   26
 51  \w     76.00 101.00   1.00    3.00    --   95.80  45.00 150.00   25
 52  \w     76.00 102.00   1.00    3.00    --   95.80  61.00 -90.00   26
 53  \w     71.00  97.00   1.00    3.00    --   95.80  61.00 120.00   26
 54  \w     65.00  91.00   1.00    3.00    --   95.80  77.00 -30.00   26
 55  \w     70.00 114.00   1.00    3.00    --   95.80 -82.00-150.00   44
 56  \w     76.00 174.00   1.00    3.00    --   95.80  45.00 -30.00   98
 57  \w     65.00  90.00   1.00    3.00    --   95.80  77.00  60.00   25
 58  \w     65.00  91.00   1.00    3.00    --   95.80  82.00 -30.00   26
 59  \w     72.00  99.00   1.00    3.00    --   95.80  56.00 146.78   27
 60  \w     76.00 139.00   1.00    3.00    --   95.80  45.00 -84.72   63
 61  \w     75.00 136.00   1.00    3.00    --   95.80  49.00 100.19   61
 62  \w     73.00 125.00   1.00    3.00    --   95.80  54.00-117.69   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1373824000
_diffrn_orient_matrix_UB_12      -0.0632472000
_diffrn_orient_matrix_UB_13      0.0647050000
_diffrn_orient_matrix_UB_21      0.1316237000
_diffrn_orient_matrix_UB_22      0.0431979000
_diffrn_orient_matrix_UB_23      0.1005113000
_diffrn_orient_matrix_UB_31      -0.1009925000
_diffrn_orient_matrix_UB_32      0.1421496000
_diffrn_orient_matrix_UB_33      -0.0017750000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1465
_diffrn_reflns_av_unetI/netI     0.0682
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            13989
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.074
_diffrn_reflns_theta_max         67.074
_diffrn_reflns_theta_min         5.770
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.712
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55349
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
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    1.266
_exptl_crystal_description       block
_exptl_crystal_F_000             360
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.26
_refine_diff_density_max         0.293
_refine_diff_density_min         -0.286
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
;
 Flack x determined using 816 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     218
_refine_ls_number_reflns         3162
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0856
_refine_ls_R_factor_gt           0.0766
_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^)+(0.1376P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2045
_refine_ls_wR_factor_ref         0.2144
_reflns_Friedel_coverage         0.861
_reflns_Friedel_fraction_full    0.981
_reflns_Friedel_fraction_max     0.981
_reflns_number_gt                2544
_reflns_number_total             3162
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc04073k2.cif
_cod_data_source_block           exp_403
_cod_database_code               1556937
_shelx_shelxl_version_number     2016/6
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C4(H4)
2.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C1(H1A,H1B), C2(H2A,H2B)
2.c Aromatic/amide H refined with riding coordinates:
 N2(H2), C5(H5), C6(H6), C17(H17), C13(H13), C10(H10), C16(H16), C15(H15),
 C11(H11), C12(H12)
2.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C)
;
_shelx_res_checksum              15036
_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 4.276
_oxdiff_exptl_absorpt_empirical_full_min 0.136