Enantioselective Hydrogenation toward Chiral 3-Aryloxy Tetrahydrofurans Enabled by Spiro Ir-PNN Catalysts Containing an Unusual 5-Substituted Chiral Oxazoline Unit
Gu, Xue-Song; Xiong, Ying; Yang, Fan; Yu, Na; Yan, Pu-Cha; Xie, Jian-Hua; Zhou, Qi-Lin; ACS Catalysis  (2022) 2206–2211; doi:10.1021/acscatal.1c05746

data_4519293
_publ_section_title
;
 Enantioselective Hydrogenation toward Chiral 3-Aryloxy Tetrahydrofurans
 Enabled by Spiro Ir-PNN Catalysts Containing an Unusual 5-Substituted
 Chiral Oxazoline Unit
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              2206
_journal_page_last               2211
_journal_paper_doi               10.1021/acscatal.1c05746
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C12 H18 O3'
_chemical_formula_sum            'C12 H18 O3'
_chemical_formula_weight         210.26
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-09-26
_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                   4.62040(10)
_cell_length_b                   7.01440(10)
_cell_length_c                   36.1467(5)
_cell_measurement_reflns_used    7052
_cell_measurement_temperature    294.15
_cell_measurement_theta_max      78.9610
_cell_measurement_theta_min      4.9360
_cell_volume                     1171.49(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 0.988
_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    -84.00  66.00   0.50    0.50    --    5.00 -16.00   8.00  300
  2  \w   -140.00  11.00   0.50    0.50    --  -50.10 -16.00   8.00  302
  3  \w   -171.00 -21.00   0.50    0.50    -- -110.00  16.00 178.00  300
  4  \w   -199.00 -49.00   0.50    0.50    -- -110.00 -16.00   8.00  300
  5  \w      8.00  36.00   0.50    0.50    --  -50.10  57.00   0.00   56
  6  \w    -71.00 -45.00   0.50    0.50    --  -50.10  57.00   0.00   52
  7  \w    -45.00 -18.00   0.50    0.50    --  -50.10  38.00 -60.00   54
  8  \w    -76.00  39.00   0.50    0.50    --  -50.10  57.00 -60.00  230
  9  \w    -81.00 -55.00   0.50    0.50    --  -50.10  38.00 -60.00   52
 10  \w   -193.00-102.00   0.50    0.50    -- -110.00 -38.00  30.00  182
 11  \w    -55.00 -29.00   0.50    0.50    -- -110.00  57.00  30.00   52
 12  \w   -137.00 -88.00   0.50    0.50    -- -110.00  72.00 -30.00   98
 13  \w   -137.00 -80.00   0.50    0.50    -- -110.00  57.00  30.00  114
 14  \w    -94.00 -68.00   0.50    0.50    -- -110.00  57.00-180.00   52
 15  \w   -123.00 -21.00   0.50    0.50    -- -110.00  38.00 150.00  204
 16  \w   -143.00 -24.00   0.50    0.50    -- -110.00  72.00 -60.00  238
;
_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      0.0060615000
_diffrn_orient_matrix_UB_12      0.0342660000
_diffrn_orient_matrix_UB_13      0.0420904000
_diffrn_orient_matrix_UB_21      -0.0713482000
_diffrn_orient_matrix_UB_22      -0.2118469000
_diffrn_orient_matrix_UB_23      0.0066679000
_diffrn_orient_matrix_UB_31      0.3255367000
_diffrn_orient_matrix_UB_32      -0.0470001000
_diffrn_orient_matrix_UB_33      0.0006737000
_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  0.0156
_diffrn_reflns_av_unetI/netI     0.0135
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -2
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            9238
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.255
_diffrn_reflns_theta_min         4.894
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.684
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54528
_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    1.192
_exptl_crystal_description       block
_exptl_crystal_F_000             456
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.129
_refine_diff_density_min         -0.102
_refine_diff_density_rms         0.030
_refine_ls_abs_structure_details
;
 Flack x determined using 878 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(6)
_refine_ls_extinction_coef       0.0081(14)
_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   1.031
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     147
_refine_ls_number_reflns         2444
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0325
_refine_ls_R_factor_gt           0.0318
_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^)+(0.0630P)^2^+0.0692P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0960
_refine_ls_wR_factor_ref         0.0966
_reflns_Friedel_coverage         0.610
_reflns_Friedel_fraction_full    0.985
_reflns_Friedel_fraction_max     0.929
_reflns_number_gt                2364
_reflns_number_total             2444
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c05746_si_002.cif
_cod_data_source_block           p20190927b
_cod_database_code               4519293
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C13H20O3
_reflns_odcompleteness_completeness 99.87
_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 Ternary CH refined with riding coordinates:
 C2(H2)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C3(H3A,H3B), C4(H4A,H4B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C10(H10)
2.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C)
;
_shelx_res_checksum              23993
_shelx_hkl_checksum              79292
_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 1.406
_oxdiff_exptl_absorpt_empirical_full_min 0.674