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_4135555
_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         'C13 H13 N O3'
_chemical_formula_sum            'C13 H13 N O3'
_chemical_formula_weight         231.24
_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             2019-12-11
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5935)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.43106(6)
_cell_length_b                   6.69750(4)
_cell_length_c                   28.04143(19)
_cell_measurement_reflns_used    8020
_cell_measurement_temperature    291.15
_cell_measurement_theta_max      79.1040
_cell_measurement_theta_min      6.3130
_cell_volume                     1207.801(16)
_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      291.15
_diffrn_detector                 PILT
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.986
_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    -86.00  40.00   0.50    0.50    --  -49.80  27.00-158.00  252
  2  \w   -139.00 -13.00   0.50    0.50    --  -49.80 -27.00  38.00  252
  3  \w   -199.00 -74.00   0.50    0.50    -- -110.00 -27.00  38.00  250
  4  \w   -146.00 -21.00   0.50    0.50    -- -110.00  27.00-158.00  250
  5  \w    -83.00  40.00   0.50    0.50    --  -49.80  72.00-120.00  246
  6  \w    -79.00  40.00   0.50    0.50    --  -49.80  57.00 120.00  238
  7  \w   -143.00 -21.00   0.50    0.50    -- -110.00  72.00   0.00  244
  8  \w   -199.00 -79.00   0.50    0.50    -- -110.00 -38.00 -60.00  240
  9  \w   -183.00 -79.00   0.50    0.50    -- -110.00 -38.00   2.41  208
 10  \w    -89.00 -63.00   0.50    0.50    -- -110.00  57.00 120.00   52
 11  \w    -48.00 -23.00   0.50    0.50    -- -110.00  57.00 120.00   50
 12  \w   -135.00 -22.00   0.50    0.50    -- -110.00  57.00   0.00  226
;
_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      -0.0417992000
_diffrn_orient_matrix_UB_12      -0.1262525000
_diffrn_orient_matrix_UB_13      -0.0449035000
_diffrn_orient_matrix_UB_21      0.0733441000
_diffrn_orient_matrix_UB_22      -0.1885004000
_diffrn_orient_matrix_UB_23      0.0266448000
_diffrn_orient_matrix_UB_31      -0.2241890000
_diffrn_orient_matrix_UB_32      -0.0379659000
_diffrn_orient_matrix_UB_33      0.0170774000
_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  0.0135
_diffrn_reflns_av_unetI/netI     0.0102
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            9645
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.361
_diffrn_reflns_theta_min         6.314
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.749
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.29244
_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    1.272
_exptl_crystal_description       block
_exptl_crystal_F_000             488
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.135
_refine_diff_density_min         -0.124
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 966 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(5)
_refine_ls_extinction_coef       0.030(2)
_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   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     174
_refine_ls_number_reflns         2534
_refine_ls_number_restraints     33
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0375
_refine_ls_R_factor_gt           0.0370
_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^)+(0.0504P)^2^+0.1502P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0994
_refine_ls_wR_factor_ref         0.0998
_reflns_Friedel_coverage         0.649
_reflns_Friedel_fraction_full    0.987
_reflns_Friedel_fraction_max     0.941
_reflns_number_gt                2483
_reflns_number_total             2534
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c11504_si_001.cif
_cod_data_source_block           p20191211a
_cod_original_cell_volume        1207.800(16)
_cod_database_code               4135555
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C13H13NO3
_shelx_estimated_absorpt_t_max   0.841
_shelx_estimated_absorpt_t_min   0.796
_reflns_odcompleteness_completeness 99.60
_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
2. Restrained distances
 C2-C6A = C2-C6
 1.52 with sigma of 0.01
 C6A-C7A = C6-C7
 1.34 with sigma of 0.01
 C2-C6 = C2-C6A
 1.52 with sigma of 0.01
 C6-C7 = C6A-C7A
 1.34 with sigma of 0.01
 C2-C7A \\sim C2-C7
 with sigma of 0.01
 C2-C7 \\sim C2-C7A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C6A) \\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C7)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C6) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C6A) \\sim Ueq, Uanis(C7A)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=1-FVAR(1)
 Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7A)=Sof(H7B)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C3(H3)
5.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B)
5.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C6(H6), C6A(H6A)
5.d X=CH2 refined with riding coordinates:
 C7(H7A,H7B), C7A(H7AA,H7AB)
;
_shelx_res_checksum              95830
_shelx_hkl_checksum              79291
_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 3.078
_oxdiff_exptl_absorpt_empirical_full_min 0.782