Coordination-Induced Stereocontrol over Carbocations: Asymmetric Reductive Deoxygenation of Racemic Tertiary Alcohols.
Isomura, Mayuko; Petrone, David A.; Carreira, Erick M.; Journal of the American Chemical Society 141 (2019) 4738–4748; doi:10.1021/jacs.9b00862

data_4128946
_publ_section_title
;
 Coordination-Induced Stereocontrol over Carbocations: Asymmetric
 Reductive Deoxygenation of Racemic Tertiary Alcohols.
;
_journal_issue                   11
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              4738
_journal_page_last               4748
_journal_paper_doi               10.1021/jacs.9b00862
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H15 Cl N2 O6'
_chemical_formula_sum            'C18 H15 Cl N2 O6'
_chemical_formula_weight         390.77
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-10-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                64.113(2)
_cell_angle_beta                 87.206(2)
_cell_angle_gamma                89.732(2)
_cell_formula_units_Z            4
_cell_length_a                   9.9297(2)
_cell_length_b                   13.7671(3)
_cell_length_c                   14.1998(4)
_cell_measurement_reflns_used    22374
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      78.9440
_cell_measurement_theta_min      4.4210
_cell_volume                     1744.00(8)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28d (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28d (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28d (Rigaku OD, 2015)'
_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      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 300K'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.964
_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     26.00 116.00   0.50    0.30    --   49.37  77.00  60.00  180
  2  \w     48.00  75.00   0.50    0.30    --   70.00  75.00 -43.57   54
  3  \w     66.00  98.00   0.50    1.20    --   82.00  58.00 -66.80   64
  4  \w     97.00 138.00   0.50    1.20    --  110.00  57.00 -30.00   82
  5  \w    133.00 175.00   0.50    1.20    --  110.00  77.00 -60.00   84
  6  \w    123.00 166.00   0.50    1.20    --  110.00  77.00  30.00   86
  7  \w    148.00 173.00   0.50    1.20    --  110.00  66.00  68.02   50
  8  \w    132.00 175.00   0.50    1.20    --  110.00  77.00 120.00   86
  9  \w    129.00 176.00   0.50    1.20    --  110.00  71.00 179.02   94
 10  \w    126.00 177.00   0.50    1.20    --  110.00  77.00  90.00  102
 11  \w    125.00 177.00   0.50    1.20    --  110.00  77.00 150.00  104
 12  \w    108.00 135.00   0.50    1.20    --  110.00  38.00 120.00   54
 13  \w     91.00 126.00   0.50    1.20    --  110.00  66.00  68.02   70
 14  \w     95.00 122.00   0.50    1.20    --  110.00  57.00  90.00   54
 15  \w    100.00 142.00   0.50    1.20    --  110.00  57.00 150.00   84
 16  \w     99.00 125.00   0.50    1.20    --  110.00  38.00  90.00   52
 17  \w     98.00 177.00   0.50    1.20    --  110.00  38.00  60.00  158
 18  \w    116.00 176.00   0.50    1.20    --  110.00  77.00   0.00  120
 19  \w     98.00 178.00   0.50    1.20    --  110.00  57.00-150.00  160
 20  \w     96.00 137.00   0.50    1.20    --  110.00  57.00-180.00   82
 21  \w     94.00 176.00   0.50    1.20    --  110.00  57.00-120.00  164
 22  \w     95.00 128.00   0.50    1.20    --  110.00  57.00 -90.00   66
 23  \w     91.00 177.00   0.50    1.20    --  110.00  77.00 -30.00  172
 24  \w     94.00 127.00   0.50    1.20    --  110.00  57.00 -60.00   66
 25  \w     87.00 114.00   0.50    1.20    --  110.00  77.00   0.00   54
 26  \w     86.00 128.00   0.50    1.20    --  110.00  77.00 -60.00   84
 27  \w     86.00 173.00   0.50    1.20    --  110.00  77.00 -90.00  174
 28  \w     98.00 145.00   0.50    1.20    --  110.00  38.00  30.00   94
 29  \w     91.00 117.00   0.50    1.20    --  110.00  77.00  90.00   52
 30  \w     86.00 127.00   0.50    1.20    --  110.00  77.00 120.00   82
 31  \w     89.00 116.00   0.50    1.20    --  110.00  71.00 179.02   54
 32  \w     86.00 113.00   0.50    1.20    --  110.00  77.00 150.00   54
 33  \w     56.00  87.00   0.50    0.30    --   78.00  73.00 143.63   62
 34  \w     34.00 121.00   0.50    0.30    --   49.37  57.00  30.00  174
 35  \w     54.00  80.00   0.50    0.30    --   74.00  69.00  44.22   52
 36  \w     86.00 119.00   0.50    1.20    --  110.00  77.00  30.00   66
 37  \w     37.00 129.00   0.50    0.30    --   62.00  80.00 138.51  184
 38  \w     34.00 121.00   0.50    0.30    --   49.37  57.00 120.00  174
 39  \w     38.00  81.00   0.50    1.20    --  110.00 -57.00  90.00   86
 40  \w     52.00  96.00   0.50    1.20    --  110.00 -99.00  60.00   88
 41  \w     68.00 120.00   0.50    1.20    --  110.00-125.00   0.00  104
 42  \w     48.00  82.00   0.50    1.20    --  110.00 -57.00-120.00   68
 43  \w     57.00 110.00   0.50    1.20    --  110.00 -99.00-180.00  106
 44  \w     46.00  85.00   0.50    1.20    --  110.00 -99.00 -90.00   78
 45  \w     48.00 111.00   0.50    1.20    --  110.00 -77.00 -30.00  126
 46  \w     41.00 104.00   0.50    1.20    --  110.00 -99.00  90.00  126
 47  \w     57.00 116.00   0.50    1.20    --  110.00-125.00 150.00  118
 48  \w     26.00 116.00   0.50    0.30    --   49.37  77.00 -60.00  180
 49  \w     86.00 125.00   0.50    1.20    --  110.00  77.00-150.00   78
 50  \w     59.00 120.00   0.50    0.30    --   49.37 178.00-180.00  122
 51  \w     37.00 129.00   0.50    0.30    --   62.00  80.00-138.14  184
 52  \w     26.00 116.00   0.50    0.30    --   49.37  77.00-150.00  180
 53  \w     26.00 116.00   0.50    0.30    --   49.37  77.00   0.00  180
 54  \w     29.00 121.00   0.50    0.30    --   54.00  80.00 103.31  184
 55  \w      2.00  46.00   0.50    0.30    --   30.00  86.00-143.57   88
 56  \w    -71.00 -45.00   0.50    1.20    --  -70.00 -80.00  55.25   52
 57  \w    -78.00 -48.00   0.50    1.20    --  -70.00 -73.00  93.36   60
 58  \w    -72.00 -46.00   0.50    1.20    --  -70.00 -77.00 150.00   52
 59  \w    -77.00 -51.00   0.50    1.20    --  -70.00 -68.00 177.56   52
 60  \w    -72.00 -46.00   0.50    1.20    --  -70.00 -77.00 120.00   52
 61  \w   -125.00 -36.00   0.50    0.30    --  -49.37 -38.00  90.00  178
 62  \w    -71.00 -46.00   0.50    1.20    --  -70.00 -77.00 -30.00   50
 63  \w    -74.00 -46.00   0.50    1.20    --  -70.00 -77.00 -90.00   56
 64  \w    -76.00 -48.00   0.50    1.20    --  -70.00 -72.00-117.82   56
 65  \w    -72.00 -46.00   0.50    1.20    --  -70.00 -77.00 -60.00   52
 66  \w    -93.00 -51.00   0.50    1.20    --  -70.00 -69.00-147.59   84
 67  \w   -121.00 -34.00   0.50    0.30    --  -49.37 -57.00-120.00  174
 68  \w    -76.00 -27.00   0.50    1.20    --  -70.00  38.00 -60.00   98
 69  \w    -95.00  -9.00   0.50    1.20    --  -70.00 125.00 -90.00  172
 70  \w   -125.00 -36.00   0.50    0.30    --  -49.37 -38.00  30.00  178
 71  \w    -52.00  41.00   0.50    0.30    --  -26.00  82.00 156.36  186
 72  \w     51.00  97.00   0.50    1.20    --  110.00 -99.00-150.00   92
 73  \w   -122.00 -35.00   0.50    0.30    --  -49.37 178.00-120.00  174
 74  \w   -125.00 -36.00   0.50    0.30    --  -49.37 -38.00 -60.00  178
 75  \w   -125.00 -31.00   0.50    0.30    --  -58.00 -83.00 -23.94  188
 76  \w   -121.00 -95.00   0.50    1.20    --  -70.00 -77.00 -90.00   52
 77  \w   -137.00 -43.00   0.50    1.20    --  -70.00 -83.00-169.63  188
 78  \w   -133.00 -42.00   0.50    1.20    --  -66.00 -77.00   2.01  182
 79  \w   -137.00 -48.00   0.50    1.20    --  -70.00 -72.00  55.08  178
 80  \w   -137.00-100.00   0.50    1.20    --  -70.00 -77.00 -60.00   74
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 300K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0172501000
_diffrn_orient_matrix_UB_12      -0.0360730000
_diffrn_orient_matrix_UB_13      0.1177410000
_diffrn_orient_matrix_UB_21      -0.0675005000
_diffrn_orient_matrix_UB_22      -0.1097001000
_diffrn_orient_matrix_UB_23      0.0250950000
_diffrn_orient_matrix_UB_31      0.1388611000
_diffrn_orient_matrix_UB_32      -0.0462718000
_diffrn_orient_matrix_UB_33      -0.0094411000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0201
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            14890
_diffrn_reflns_point_group_measured_fraction_full 0.950
_diffrn_reflns_point_group_measured_fraction_max 0.892
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.650
_diffrn_reflns_theta_min         3.464
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.302
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.719
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28d (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.488
_exptl_crystal_description       plate
_exptl_crystal_F_000             808
_exptl_crystal_size_max          0.125
_exptl_crystal_size_mid          0.097
_exptl_crystal_size_min          0.032
_refine_diff_density_max         0.294
_refine_diff_density_min         -0.254
_refine_diff_density_rms         0.047
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.011(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     974
_refine_ls_number_reflns         14890
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0390
_refine_ls_R_factor_gt           0.0369
_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^)+(0.0630P)^2^+0.3917P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0990
_refine_ls_wR_factor_ref         0.1008
_reflns_Friedel_coverage         0.852
_reflns_Friedel_fraction_full    0.903
_reflns_Friedel_fraction_max     0.821
_reflns_number_gt                14152
_reflns_number_total             14890
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.9960\% 
 around [1.00 0.00 0.07] (reciprocal) or [1.00 -0.00 0.00] (direct)
;
_cod_data_source_file            ja9b00862_si_004.cif
_cod_data_source_block           ca021018_1_1_twin1_hklf4
_cod_database_code               4128946
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C18H15ClN2O6
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.7278(16)
 0.2722(16)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3.a Ternary CH refined with riding coordinates:
 C7A(H7A), C8A(H8A), C7B(H7B), C8B(H8B), C7C(H7C), C8C(H8C), C7D(H7D), C8D(H8D)
3.b Secondary CH2 refined with riding coordinates:
 C9A(H9AA,H9AB), C10A(H10A,H10B), C11A(H11A,H11B), C9B(H9BA,H9BB), C10B(H10C,
 H10D), C11B(H11C,H11D), C9C(H9CA,H9CB), C10C(H10E,H10F), C11C(H11E,H11F),
 C9D(H9DA,H9DB), C10D(H10G,H10H), C11D(H11G,H11H)
3.c Aromatic/amide H refined with riding coordinates:
 C2A(H2A), C3A(H3A), C5A(H5A), C6A(H6A), C14A(H14A), C16A(H16A), C18A(H18A),
 C2B(H2B), C3B(H3B), C5B(H5B), C6B(H6B), C14B(H14B), C16B(H16B), C18B(H18B),
 C2C(H2C), C3C(H3C), C5C(H5C), C6C(H6C), C14C(H14C), C16C(H16C), C18C(H18C),
 C2D(H2D), C3D(H3D), C5D(H5D), C6D(H6D), C14D(H14D), C16D(H16D), C18D(H18D)
;
_shelx_res_checksum              94503
_shelx_hkl_checksum              48089
_olex2_date_sample_data_collection 2018-10-03
_olex2_date_sample_submission    2018-10-03
_olex2_submission_original_sample_id ca021018_1_1
_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 1.215
_oxdiff_exptl_absorpt_empirical_full_min 0.766
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2