Palladium/GF-Phos-catalyzed asymmetric carbenylative amination to access chiral pyrrolidines and piperidines
Sun, Yue; Ma, Chun; Li, Zhiming; Zhang, Junliang; Chemical Science 13 (2022) 11150–11155; doi:10.1039/D2SC03999K

data_1567608
_publ_section_title
;
 Palladium/GF-Phos-catalyzed asymmetric carbenylative amination to access
 chiral pyrrolidines and piperidines
;
_journal_issue                   37
_journal_name_full               'Chemical Science'
_journal_page_first              11150
_journal_page_last               11155
_journal_paper_doi               10.1039/D2SC03999K
_journal_volume                  13
_journal_year                    2022
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C23 H29 N'
_chemical_formula_sum            'C23 H29 N'
_chemical_formula_weight         319.47
_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             2021-11-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-12-17 deposited with the CCDC.	2022-09-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.500(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.9102(3)
_cell_length_b                   6.1038(2)
_cell_length_c                   14.7452(4)
_cell_measurement_reflns_used    8288
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      73.5300
_cell_measurement_theta_min      4.6700
_cell_volume                     968.47(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_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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     35.00  61.00   1.00    1.00    --    0.00  37.00  30.00   26
  2  \w    -18.00  14.00   1.00    1.00    --    0.00  37.00  30.00   32
  3  \w    -18.00  51.00   1.00    1.00    --    0.00  37.00-180.00   69
  4  \w    -18.00  37.00   1.00    1.00    --    0.00  37.00 -90.00   55
  5  \w     60.00  89.00   1.00    1.00    --    0.00  37.00-180.00   29
  6  \w     12.00  62.00   1.00    1.00    --    0.00  57.00 -30.00   50
  7  \w    -23.00   8.00   1.00    1.00    --    0.00  57.00 -30.00   31
  8  \w    -15.00  80.00   1.00    1.00    --    0.00  37.00  60.00   95
  9  \w      3.00  56.00   1.00    1.00    --    0.00  82.00-150.00   53
 10  \w     42.00  85.00   1.00    1.00    --    0.00  37.00 -90.00   43
 11  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  47.14   25
 12  \w     71.00  98.00   1.00    1.00    --   95.80  61.00   0.00   27
 13  \w     75.00 185.00   1.00    1.00    --   95.80  45.00 -60.00  110
 14  \w     65.00  91.00   1.00    1.00    --   95.80  77.00-180.00   26
 15  \w     78.00 183.00   1.00    1.00    --   95.80  45.00 120.00  105
 16  \w    131.00 184.00   1.00    1.00    --   95.80  81.00 138.63   53
 17  \w    149.00 175.00   1.00    1.00    --   95.80  56.00-132.60   26
 18  \w     55.00 106.00   1.00    1.00    --   95.80 -82.00 150.00   51
 19  \w     86.00 128.00   1.00    1.00    --   95.80 -82.00  90.00   42
 20  \w     27.00  68.00   1.00    1.00    --   95.80 -82.00  90.00   41
 21  \w     30.00  98.00   1.00    1.00    --   95.80 -82.00 -90.00   68
 22  \w     63.00  90.00   1.00    1.00    --   95.80  82.00-120.00   27
 23  \w     74.00 100.00   1.00    1.00    --   95.80  61.00  30.00   26
 24  \w    153.00 179.00   1.00    1.00    --   95.80  78.00 -34.37   26
 25  \w     71.00  97.00   1.00    1.00    --   95.80  61.00-150.00   26
 26  \w    153.00 184.00   1.00    1.00    --   95.80  61.00   0.00   31
 27  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  30.00   25
 28  \w     65.00  93.00   1.00    1.00    --   95.80  77.00  90.00   28
 29  \w     71.00  97.00   1.00    1.00    --   95.80  61.00 -30.00   26
 30  \w    127.00 184.00   1.00    1.00    --   95.80  61.00 -30.00   57
 31  \w     63.00  89.00   1.00    1.00    --   95.80  81.00 138.63   26
 32  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 -60.00   25
 33  \w     65.00  90.00   1.00    1.00    --   95.80  77.00   0.00   25
 34  \w     50.00 126.00   1.00    1.00    --   95.80 -82.00  60.00   76
 35  \w    106.00 185.00   1.00    1.00    --   95.80  82.00  60.00   79
 36  \w     65.00  91.00   1.00    1.00    --   95.80  78.00 -34.37   26
 37  \w     75.00 179.00   1.00    1.00    --   95.80  45.00-150.00  104
 38  \w     71.00 118.00   1.00    1.00    --   95.80  61.00  60.00   47
 39  \w     74.00 100.00   1.00    1.00    --   95.80  61.00 150.00   26
 40  \w     65.00  91.00   1.00    1.00    --   95.80  77.00-120.00   26
 41  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 -90.00   26
 42  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  60.00   25
 43  \w     63.00  89.00   1.00    1.00    --   95.80  82.00  90.00   26
 44  \w      6.00  46.00   1.00    1.00    --   95.80 -82.00  60.00   40
 45  \w    140.00 166.00   1.00    1.00    --   95.80  81.00 -78.39   26
 46  \w     78.00 178.00   1.00    1.00    --   95.80  45.00 -90.00  100
 47  \w     76.00 112.00   1.00    1.00    --   95.80  45.00   0.00   36
 48  \w    133.00 184.00   1.00    1.00    --   95.80  45.00   0.00   51
 49  \w     64.00 100.00   1.00    1.00    --   95.80  82.00  60.00   36
 50  \w     63.00  89.00   1.00    1.00    --   95.80  81.00 -78.39   26
 51  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 120.00   26
 52  \w     66.00  92.00   1.00    1.00    --   95.80  77.00-150.00   26
 53  \w     63.00 100.00   1.00    1.00    --   95.80  82.00 150.00   37
 54  \w      7.00 127.00   1.00    1.00    --   95.80 -82.00   0.00  120
 55  \w    104.00 129.00   1.00    1.00    --   95.80  77.00-180.00   25
 56  \w    117.00 159.00   1.00    1.00    --   95.80  77.00  47.14   42
 57  \w     75.00 141.00   1.00    1.00    --   95.80  46.00  36.08   66
 58  \w     72.00  98.00   1.00    1.00    --   95.80  56.00-132.60   26
 59  \w     76.00 102.00   1.00    1.00    --   95.80  30.00-150.00   26
 60  \w     75.00 102.00   1.00    1.00    --   95.80  45.00 150.00   27
 61  \w    106.00 136.00   1.00    1.00    --   95.80  45.00 150.00   30
 62  \w     47.00 117.00   1.00    1.00    --   95.80 -82.00-120.00   70
 63  \w     75.00 100.00   1.00    1.00    --   95.80  44.00 -97.61   25
;
_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      0.1192207000
_diffrn_orient_matrix_UB_12      -0.0292136000
_diffrn_orient_matrix_UB_13      0.0711026000
_diffrn_orient_matrix_UB_21      -0.0765047000
_diffrn_orient_matrix_UB_22      -0.1061448000
_diffrn_orient_matrix_UB_23      0.0672893000
_diffrn_orient_matrix_UB_31      0.0203443000
_diffrn_orient_matrix_UB_32      -0.2272275000
_diffrn_orient_matrix_UB_33      -0.0404849000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0629
_diffrn_reflns_av_unetI/netI     0.0387
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            19273
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.058
_diffrn_reflns_theta_max         67.058
_diffrn_reflns_theta_min         4.108
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.467
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51262
_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    1.096
_exptl_crystal_description       block
_exptl_crystal_F_000             348
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.370
_refine_diff_density_min         -0.175
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 1296 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.1(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     220
_refine_ls_number_reflns         3408
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0491
_refine_ls_R_factor_gt           0.0465
_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^)+(0.0854P)^2^+0.0894P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1281
_refine_ls_wR_factor_ref         0.1301
_reflns_Friedel_coverage         0.792
_reflns_Friedel_fraction_full    0.970
_reflns_Friedel_fraction_max     0.970
_reflns_number_gt                3177
_reflns_number_total             3408
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc03999k2.cif
_cod_data_source_block           exp_2405
_cod_depositor_comments          'Adding full bibliography for 1567608.cif.'
_cod_database_code               1567608
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.946
_shelx_estimated_absorpt_t_min   0.843
_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.a Ternary CH refined with riding coordinates:
 C8(H8)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C12(H12), C13(H13), C15(H15),
 C16(H16), C18(H18), C19(H19)
2.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              48844
_shelx_hkl_checksum              57584
_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 1.814
_oxdiff_exptl_absorpt_empirical_full_min 0.608