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_4128947
_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_formula_moiety         'C17 H27 N O4'
_chemical_formula_sum            'C17 H27 N O4'
_chemical_formula_weight         309.39
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-04-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.18 svn.r3501 for OlexSys, GUI svn.r5488)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.1556(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.03546(5)
_cell_length_b                   17.81899(11)
_cell_length_c                   11.97478(7)
_cell_measurement_reflns_used    47325
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      79.4510
_cell_measurement_theta_min      3.7220
_cell_volume                     1704.709(18)
_computing_cell_refinement       'CrysAlisPro 1.171.39.31d (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.31d (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.31d (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      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 300K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_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     33.00 121.00   0.50    0.10    --   54.00  72.00  94.50  176
  2  \w     57.00 146.00   0.50    0.10    --   78.00  71.00 106.45  178
  3  \w     75.00 162.00   0.50    0.14    --   90.00  56.00 112.45  174
  4  \w     60.00 148.00   0.50    0.10    --   78.00  64.00   0.92  176
  5  \w     71.00 159.00   0.50    0.14    --   90.00  67.00-175.22  176
  6  \w     87.00 176.00   0.50    0.14    --  110.00  75.00-139.32  178
  7  \w     86.00 177.00   0.50    0.14    --  110.00  77.00-120.00  182
  8  \w     86.00 126.00   0.50    0.14    --  110.00  77.00 -90.00   80
  9  \w     94.00 178.00   0.50    0.14    --  110.00  57.00-150.00  168
 10  \w    130.00 174.00   0.50    0.14    --  110.00  77.00 -90.00   88
 11  \w     86.00 177.00   0.50    0.14    --  110.00  77.00   0.00  182
 12  \w     99.00 149.00   0.50    0.14    --  110.00  38.00 -60.00  100
 13  \w    111.00 152.00   0.50    0.14    --  110.00  38.00 -90.00   82
 14  \w     98.00 178.00   0.50    0.14    --  110.00  38.00  30.00  160
 15  \w     86.00 163.00   0.50    0.14    --  110.00  77.00  60.00  154
 16  \w     87.00 120.00   0.50    0.14    --  110.00  77.00  90.00   66
 17  \w     96.00 177.00   0.50    0.14    --  110.00  57.00 150.00  162
 18  \w     86.00 173.00   0.50    0.14    --  110.00  77.00 120.00  174
 19  \w     94.00 178.00   0.50    0.14    --  110.00  57.00 120.00  168
 20  \w    124.00 175.00   0.50    0.14    --  110.00  77.00  90.00  102
 21  \w    133.00 168.00   0.50    0.14    --  110.00  77.00 -30.00   70
 22  \w     86.00 112.00   0.50    0.14    --  110.00  77.00 -30.00   52
 23  \w     99.00 157.00   0.50    0.14    --  110.00  38.00   0.00  116
 24  \w     86.00 173.00   0.50    0.14    --  110.00  77.00  30.00  174
 25  \w     59.00 120.00   0.50    0.10    --   49.37 178.00  90.00  122
 26  \w    -57.00  37.00   0.50    0.10    --  -30.00  84.00-105.29  188
 27  \w    -95.00  -9.00   0.50    0.14    --  -70.00 125.00 120.00  172
 28  \w     12.00  38.00   0.50    0.10    --   38.00  83.00-124.59   52
 29  \w     86.00 169.00   0.50    0.14    --  110.00  77.00 -60.00  166
 30  \w     86.00 112.00   0.50    0.14    --  110.00  77.00-150.00   52
 31  \w     96.00 132.00   0.50    0.14    --  110.00  57.00-180.00   72
 32  \w    152.00 177.00   0.50    0.14    --  110.00  57.00-180.00   50
 33  \w     14.00 103.00   0.50    0.10    --   34.00  68.00-143.03  178
 34  \w     13.00  43.00   0.50    0.10    --   38.00  80.00  37.63   60
 35  \w     41.00  84.00   0.50    0.14    --  110.00 -57.00   0.00   86
 36  \w     44.00 134.00   0.50    0.14    --  110.00 -77.00  30.00  180
 37  \w     38.00  84.00   0.50    0.14    --  110.00 -57.00-120.00   92
 38  \w     38.00  84.00   0.50    0.14    --  110.00 -57.00 150.00   92
 39  \w   -117.00 -28.00   0.50    0.10    --  -50.00 -73.00-162.76  178
 40  \w   -125.00 -36.00   0.50    0.10    --  -49.37 -38.00  30.00  178
 41  \w   -125.00 -36.00   0.50    0.10    --  -49.37 -38.00 120.00  178
 42  \w   -125.00 -37.00   0.50    0.10    --  -49.37 -19.00 150.00  176
 43  \w     40.00 110.00   0.50    0.14    --  110.00 -99.00  60.00  140
 44  \w     40.00 110.00   0.50    0.14    --  110.00 -99.00   0.00  140
 45  \w     39.00 122.00   0.50    0.14    --  110.00-125.00 -90.00  166
 46  \w     40.00 110.00   0.50    0.14    --  110.00 -99.00-180.00  140
 47  \w     46.00  95.00   0.50    0.14    --  110.00 -99.00 -90.00   98
 48  \w     80.00 106.00   0.50    0.14    --  110.00 -99.00 120.00   52
 49  \w     57.00 107.00   0.50    0.14    --  110.00 -99.00 -30.00  100
 50  \w   -121.00 -32.00   0.50    0.10    --  -54.00 -73.00 -62.88  178
 51  \w   -122.00 -33.00   0.50    0.10    --  -54.00 -70.00 158.58  178
 52  \w   -125.00 -36.00   0.50    0.10    --  -58.00 -72.00 129.77  178
 53  \w   -129.00 -40.00   0.50    0.14    --  -62.00 -73.00   1.81  178
 54  \w   -133.00 -44.00   0.50    0.14    --  -66.00 -72.00-165.52  178
 55  \w   -137.00 -49.00   0.50    0.14    --  -70.00 -71.00-169.30  176
 56  \w   -137.00 -48.00   0.50    0.14    --  -70.00 -72.00-130.05  178
 57  \w   -138.00 -49.00   0.50    0.14    --  -70.00 -70.00 -92.79  178
 58  \w   -138.00 -49.00   0.50    0.14    --  -70.00 -69.00  10.08  178
 59  \w   -138.00 -49.00   0.50    0.14    --  -70.00 -69.00 -73.48  178
 60  \w   -138.00 -49.00   0.50    0.14    --  -70.00 -70.00-111.52  178
 61  \w   -139.00 -50.00   0.50    0.14    --  -70.00 -67.00 134.08  178
 62  \w   -137.00 -48.00   0.50    0.14    --  -70.00 -72.00  77.23  178
 63  \w   -137.00 -48.00   0.50    0.14    --  -70.00 -72.00  40.34  178
 64  \w   -138.00 -50.00   0.50    0.14    --  -70.00 -68.00  59.46  176
 65  \w   -137.00 -49.00   0.50    0.14    --  -70.00 -71.00 -41.77  176
 66  \w   -137.00 -49.00   0.50    0.14    --  -70.00 -71.00 107.97  176
 67  \w   -137.00 -48.00   0.50    0.14    --  -70.00 -73.00 163.45  178
 68  \w   -137.00 -48.00   0.50    0.14    --  -70.00 -73.00 -23.44  178
;
_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      -0.0279210000
_diffrn_orient_matrix_UB_12      0.0421879000
_diffrn_orient_matrix_UB_13      -0.1127390000
_diffrn_orient_matrix_UB_21      0.1590912000
_diffrn_orient_matrix_UB_22      0.0467161000
_diffrn_orient_matrix_UB_23      0.0329852000
_diffrn_orient_matrix_UB_31      0.1053880000
_diffrn_orient_matrix_UB_32      -0.0592652000
_diffrn_orient_matrix_UB_33      -0.0542298000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0402
_diffrn_reflns_av_unetI/netI     0.0123
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            63305
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.846
_diffrn_reflns_theta_min         4.466
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.689
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.412
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.31d (Rigaku Oxford Diffraction, 2017)
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    1.206
_exptl_crystal_description       block
_exptl_crystal_F_000             672
_exptl_crystal_size_max          0.268
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.153
_refine_diff_density_max         0.630
_refine_diff_density_min         -0.378
_refine_diff_density_rms         0.043
_refine_ls_extinction_coef       0.0013(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     209
_refine_ls_number_reflns         3691
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0403
_refine_ls_R_factor_gt           0.0385
_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^)+(0.0531P)^2^+0.7297P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1022
_refine_ls_wR_factor_ref         0.1035
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3469
_reflns_number_total             3691
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b00862_si_002.cif
_cod_data_source_block           ca190418_1_1
_cod_original_cell_volume        1704.708(18)
_cod_database_code               4128947
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C17H27NO4
_reflns_odcompleteness_completeness 99.97
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-H1
 0.93 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C6(H6), C10(H10)
3.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C14(H14A,H14B), C16(H16A,H16B)
3.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C11(H11A,H11B,H11C),
 C12(H12A,H12B,H12C), C17(H17A,H17B,H17C)
;
_shelx_res_checksum              66516
_shelx_hkl_checksum              4149
_olex2_submission_original_sample_id ca190418_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.431
_oxdiff_exptl_absorpt_empirical_full_min 0.806