Enantioselective Inverse Electron Demand (3 + 2) Cycloaddition of Palladium-Oxyallyl Enabled by a Hydrogen-Bond-Donating Ligand.
Zheng, Yin; Qin, Tianzhu; Zi, Weiwei; Journal of the American Chemical Society 143 (2021) 1038–1045; doi:10.1021/jacs.0c11504

data_4135553
_publ_section_title
;
 Enantioselective Inverse Electron Demand (3 + 2) Cycloaddition of
 Palladium-Oxyallyl Enabled by a Hydrogen-Bond-Donating Ligand.
;
_journal_issue                   2
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              1038
_journal_page_last               1045
_journal_paper_doi               10.1021/jacs.0c11504
_journal_volume                  143
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C16 H19 N O3'
_chemical_formula_sum            'C16 H19 N O3'
_chemical_formula_weight         273.32
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-06-15
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.12450(10)
_cell_length_b                   10.73560(10)
_cell_length_c                   19.33040(10)
_cell_measurement_reflns_used    9088
_cell_measurement_temperature    294.15
_cell_measurement_theta_max      78.7040
_cell_measurement_theta_min      4.5800
_cell_volume                     1478.50(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      294.15
_diffrn_detector                 PILT
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.985
_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  94.00   0.50    0.50    --    5.00  65.00-135.00  240
  2  \w    -84.00  34.00   0.50    0.50    --    5.00 -56.00-106.00  236
  3  \w    -79.00  40.00   0.50    0.50    --  -49.60  56.00  36.00  238
  4  \w   -139.00 -20.00   0.50    0.50    --  -49.60 -56.00-106.00  238
  5  \w   -139.00 -72.00   0.50    0.50    --  -49.60 -65.00  89.00  134
  6  \w   -163.00-138.00   0.50    0.50    -- -110.00 -65.00  89.00   50
  7  \w   -105.00 -80.00   0.50    0.50    -- -110.00  65.00-135.00   50
  8  \w   -104.00 -79.00   0.50    0.50    -- -110.00  56.00  36.00   50
  9  \w   -164.00-139.00   0.50    0.50    -- -110.00 -56.00-106.00   50
 10  \w     21.00  46.00   0.50    0.50    --    5.00  57.00 -90.00   50
 11  \w   -139.00 -19.00   0.50    0.50    --  -49.60 -38.00-180.00  240
 12  \w   -139.00 -68.00   0.50    0.50    -- -110.00  72.00 -90.00  142
 13  \w   -169.00-143.00   0.50    0.50    -- -110.00 -72.00-120.00   52
 14  \w   -141.00-115.00   0.50    0.50    -- -110.00 -72.00-120.00   52
 15  \w   -199.00-138.00   0.50    0.50    -- -110.00 -57.00   0.00  122
 16  \w   -139.00 -21.00   0.50    0.50    -- -110.00  57.00  90.00  236
 17  \w   -151.00 -83.00   0.50    0.50    -- -110.00 -57.00-180.00  136
 18  \w   -181.00-140.00   0.50    0.50    -- -110.00 -57.00-120.00   82
 19  \w   -133.00 -81.00   0.50    0.50    -- -110.00 -57.00-120.00  104
 20  \w   -192.00-165.00   0.50    0.50    -- -110.00 -57.00-180.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RCD3): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1177872000
_diffrn_orient_matrix_UB_12      0.0994556000
_diffrn_orient_matrix_UB_13      0.0376935000
_diffrn_orient_matrix_UB_21      0.0827414000
_diffrn_orient_matrix_UB_22      -0.0426477000
_diffrn_orient_matrix_UB_23      0.0697347000
_diffrn_orient_matrix_UB_31      0.1613871000
_diffrn_orient_matrix_UB_32      0.0942192000
_diffrn_orient_matrix_UB_33      -0.0082549000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0171
_diffrn_reflns_av_unetI/netI     0.0114
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            11352
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.343
_diffrn_reflns_theta_min         4.575
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.686
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49902
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.228
_exptl_crystal_description       block
_exptl_crystal_F_000             584
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.167
_refine_diff_density_min         -0.096
_refine_diff_density_rms         0.024
_refine_ls_abs_structure_details
;
 Flack x determined using 1146 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.03(5)
_refine_ls_extinction_coef       0.0065(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     183
_refine_ls_number_reflns         3031
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0312
_refine_ls_R_factor_gt           0.0305
_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^)+(0.0442P)^2^+0.1285P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0854
_refine_ls_wR_factor_ref         0.0859
_reflns_Friedel_coverage         0.656
_reflns_Friedel_fraction_full    0.964
_reflns_Friedel_fraction_max     0.893
_reflns_number_gt                2948
_reflns_number_total             3031
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c11504_si_004.cif
_cod_data_source_block           p2020615b
_cod_database_code               4135553
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C16H19NO3
_shelx_estimated_absorpt_t_max   0.853
_shelx_estimated_absorpt_t_min   0.810
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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 Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B), C8(H8A,H8B), C9(H9A,H9B)
2.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15)
2.c X=CH2 refined with riding coordinates:
 C7(H7A,H7B)
2.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C)
;
_shelx_res_checksum              56403
_shelx_hkl_checksum              58185
_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 1.632
_oxdiff_exptl_absorpt_empirical_full_min 0.787