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_1556939
_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_formula_moiety         'C22 H24 F N O4'
_chemical_formula_sum            'C22 H24 F N O4'
_chemical_formula_weight         385.42
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-12-07
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-01-27 deposited with the CCDC.	2019-10-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.239(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.4515(2)
_cell_length_b                   13.8216(2)
_cell_length_c                   13.0859(2)
_cell_measurement_reflns_used    16685
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      73.8540
_cell_measurement_theta_min      3.9000
_cell_volume                     2062.56(6)
_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 0.976
_diffrn_measured_fraction_theta_max 0.976
_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    -43.00 -13.00   1.00    1.00    --    0.00 -51.00 -94.00   30
  2  \w    -19.00  86.00   1.00    1.00    --    0.00  51.00  52.00  105
  3  \w    105.00 131.00   1.00    2.00    --   95.80  51.00  52.00   26
  4  \w     72.00 111.00   1.00    2.00    --   95.80 -51.00 -94.00   39
  5  \w    -11.00  15.00   1.00    1.00    --    0.00  77.00-150.00   26
  6  \w     29.00  62.00   1.00    1.00    --    0.00  19.00  60.00   33
  7  \w     25.00  89.00   1.00    1.00    --    0.00  38.00 -30.00   64
  8  \w     23.00  89.00   1.00    1.00    --    0.00  77.00-150.00   66
  9  \w    -21.00   9.00   1.00    1.00    --    0.00  19.00  60.00   30
 10  \w    -31.00  82.00   1.00    1.00    --    0.00  82.00 -90.00  113
 11  \w    -22.00  47.00   1.00    1.00    --    0.00  57.00-150.00   69
 12  \w    -15.00  11.00   1.00    1.00    --    0.00  38.00 -30.00   26
 13  \w    -19.00  66.00   1.00    1.00    --    0.00  38.00 150.00   85
 14  \w     63.00  95.00   1.00    2.00    --   95.80  82.00 -60.00   32
 15  \w     63.00  93.00   1.00    2.00    --   95.80  82.00 -90.00   30
 16  \w     98.00 124.00   1.00    2.00    --   95.80  82.00 150.00   26
 17  \w    150.00 183.00   1.00    2.00    --   95.80  82.00 -90.00   33
 18  \w     64.00  90.00   1.00    2.00    --   95.80  82.00  90.00   26
 19  \w     29.00 122.00   1.00    2.00    --   95.80 -82.00  90.00   93
 20  \w    160.00 185.00   1.00    2.00    --   95.80  82.00-120.00   25
 21  \w     64.00  90.00   1.00    2.00    --   95.80  82.00 150.00   26
 22  \w     75.00 184.00   1.00    2.00    --   95.80  45.00 -30.00  109
 23  \w     63.00  88.00   1.00    2.00    --   95.80  82.00  30.00   25
 24  \w     65.00  90.00   1.00    2.00    --   95.80  77.00   0.00   25
 25  \w     64.00  90.00   1.00    2.00    --   95.80  82.00 137.19   26
 26  \w     67.00  92.00   1.00    2.00    --   95.80  71.00  22.06   25
 27  \w    143.00 185.00   1.00    2.00    --   95.80  71.00  22.06   42
 28  \w     65.00  90.00   1.00    2.00    --   95.80  77.00-155.48   25
 29  \w    127.00 171.00   1.00    2.00    --   95.80  77.00-155.48   44
 30  \w     71.00  98.00   1.00    2.00    --   95.80  58.00 134.64   27
 31  \w     68.00  96.00   1.00    2.00    --   95.80  68.00  66.08   28
 32  \w      6.00 126.00   1.00    2.00    --   95.80 -77.00 150.00  120
 33  \w     75.00 109.00   1.00    2.00    --   95.80  45.00 -60.00   34
 34  \w     65.00  90.00   1.00    2.00    --   95.80  77.00-180.00   25
 35  \w    159.00 185.00   1.00    2.00    --   95.80  77.00 -30.00   26
 36  \w     67.00 184.00   1.00    2.00    --   95.80  72.00  73.82  117
 37  \w     65.00  99.00   1.00    2.00    --   95.80  77.00  30.00   34
 38  \w    159.00 185.00   1.00    2.00    --   95.80  77.00 -60.00   26
 39  \w     71.00 184.00   1.00    2.00    --   95.80  60.00-109.45  113
 40  \w    120.00 180.00   1.00    2.00    --   95.80  82.00-180.00   60
 41  \w     73.00 184.00   1.00    2.00    --   95.80  52.00  -5.92  111
 42  \w     76.00 153.00   1.00    2.00    --   95.80  45.00 121.25   77
 43  \w     71.00 185.00   1.00    2.00    --   95.80  61.00 139.59  114
 44  \w     65.00  90.00   1.00    2.00    --   95.80  77.00-120.00   25
 45  \w     65.00  90.00   1.00    2.00    --   95.80  77.00 -90.00   25
 46  \w     75.00 107.00   1.00    2.00    --   95.80  45.00-180.00   32
 47  \w     75.00 185.00   1.00    2.00    --   95.80  45.00-141.30  110
 48  \w     72.00  98.00   1.00    2.00    --   95.80  61.00-180.00   26
 49  \w     65.00  90.00   1.00    2.00    --   95.80  76.00  24.07   25
 50  \w     63.00  89.00   1.00    2.00    --   95.80  81.00  42.42   26
 51  \w     65.00 126.00   1.00    2.00    --   95.80  77.00-150.00   61
 52  \w     63.00  88.00   1.00    2.00    --   95.80  82.00 -30.00   25
 53  \w     75.00 177.00   1.00    2.00    --   95.80  45.00  30.00  102
 54  \w     65.00  90.00   1.00    2.00    --   95.80  77.00 -60.00   25
 55  \w     63.00  88.00   1.00    2.00    --   95.80  82.00-150.00   25
 56  \w     15.00 128.00   1.00    2.00    --   95.80 -82.00 -60.00  113
 57  \w     63.00  88.00   1.00    2.00    --   95.80  82.00 120.00   25
 58  \w     65.00  90.00   1.00    2.00    --   95.80  77.00  90.00   25
 59  \w     22.00 123.00   1.00    2.00    --   95.80 -82.00-120.00  101
 60  \w     18.00 128.00   1.00    2.00    --   95.80 -82.00   0.00  110
 61  \w     63.00  88.00   1.00    2.00    --   95.80  82.00-180.00   25
 62  \w     65.00  91.00   1.00    2.00    --   95.80  77.00 -30.00   26
 63  \w    123.00 148.00   1.00    2.00    --   95.80  82.00-120.00   25
 64  \w     64.00  90.00   1.00    2.00    --   95.80  82.00-120.00   26
;
_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      0.0204071000
_diffrn_orient_matrix_UB_12      -0.0643684000
_diffrn_orient_matrix_UB_13      0.0960446000
_diffrn_orient_matrix_UB_21      0.1317049000
_diffrn_orient_matrix_UB_22      0.0247536000
_diffrn_orient_matrix_UB_23      0.0077115000
_diffrn_orient_matrix_UB_31      -0.0222287000
_diffrn_orient_matrix_UB_32      0.0875542000
_diffrn_orient_matrix_UB_33      0.0684713000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0784
_diffrn_reflns_av_unetI/netI     0.0289
_diffrn_reflns_Laue_measured_fraction_full 0.976
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            46251
_diffrn_reflns_point_group_measured_fraction_full 0.976
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.043
_diffrn_reflns_theta_max         67.043
_diffrn_reflns_theta_min         3.876
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.753
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73113
_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    1.241
_exptl_crystal_description       block
_exptl_crystal_F_000             816
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.31
_exptl_crystal_size_min          0.21
_refine_diff_density_max         1.706
_refine_diff_density_min         -0.510
_refine_diff_density_rms         0.080
_refine_ls_extinction_coef       0.0070(12)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     257
_refine_ls_number_reflns         3604
_refine_ls_number_restraints     21
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.1179
_refine_ls_R_factor_gt           0.1146
_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^)+(0.1470P)^2^+3.7850P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3172
_refine_ls_wR_factor_ref         0.3195
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3315
_reflns_number_total             3604
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc04073k2.cif
_cod_data_source_block           exp_148
_cod_database_code               1556939
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.858
_shelx_estimated_absorpt_t_min   0.728
_reflns_odcompleteness_completeness 99.95
_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
2. Restrained distances
 C9-C19
 1.52 with sigma of 0.01
3. Rigid bond restraints
 C19, C20
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C9, C19
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
C19 \\sim C20: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C20) \\sim Ueq, Uanis(C19) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
5.a Ternary CH refined with riding coordinates:
 C2(H2), C7(H7), C9(H9)
5.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C6(H6A,H6B), C19(H19A,H19B)
5.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C14(H14), C15(H15), C17(H17), C18(H18)
5.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C)
;
_shelx_res_checksum              4973
_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 2.269
_oxdiff_exptl_absorpt_empirical_full_min 0.481