Iridium-Catalyzed Enantioselective Allylic Substitution with Aqueous Solutions of Nucleophiles.
Sandmeier, Tobias; Goetzke, F. Wieland; Krautwald, Simon; Carreira, Erick M.; Journal of the American Chemical Society 141 (2019) 12212–12218; doi:10.1021/jacs.9b05830

data_4128621
_publ_section_title
;
 Iridium-Catalyzed Enantioselective Allylic Substitution with Aqueous
 Solutions of Nucleophiles.
;
_journal_issue                   31
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              12212
_journal_page_last               12218
_journal_paper_doi               10.1021/jacs.9b05830
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C14 H20 O2'
_chemical_formula_sum            'C14 H20 O2'
_chemical_formula_weight         220.30
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-04-04
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.7750(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.71250(10)
_cell_length_b                   7.90530(10)
_cell_length_c                   15.48200(10)
_cell_measurement_reflns_used    32678
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      79.2300
_cell_measurement_theta_min      4.6810
_cell_volume                     1295.75(2)
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (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 0.998
_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      6.00  33.00   0.50    0.10    --   34.00  87.00 -77.48   54
  2  \w      7.00  36.00   0.50    0.10    --   34.00  85.00-113.85   58
  3  \w      4.00  30.00   0.50    0.10    --   34.00  90.00-171.01   52
  4  \w     24.00 113.00   0.50    0.10    --   46.00  73.00-115.72  178
  5  \w     21.00 109.00   0.50    0.10    --   42.00  72.00   1.82  176
  6  \w     21.00 109.00   0.50    0.10    --   42.00  72.00  78.83  176
  7  \w      6.00  34.00   0.50    0.10    --   34.00  86.00 163.46   56
  8  \w   -124.00 -36.00   0.50    0.10    --  -49.12 -38.00  60.00  176
  9  \w   -124.00 -36.00   0.50    0.10    --  -49.12 -38.00 -30.00  176
 10  \w     37.00 125.00   0.50    0.10    --   49.12  19.00-150.00  176
 11  \w     37.00 125.00   0.50    0.10    --   49.12  19.00 120.00  176
 12  \w     59.00 120.00   0.50    0.10    --   49.12 178.00 150.00  122
 13  \w     29.00 117.00   0.50    0.10    --   50.00  72.00 176.86  176
 14  \w     36.00 125.00   0.50    0.10    --   58.00  73.00  99.88  178
 15  \w   -137.00 -48.00   0.50    0.33    --  -70.00 -73.00 138.85  178
 16  \w   -129.00 -41.00   0.50    0.33    --  -62.00 -71.00 -84.29  176
 17  \w   -133.00 -44.00   0.50    0.33    --  -66.00 -72.00-122.98  178
 18  \w   -137.00 -48.00   0.50    0.33    --  -70.00 -73.00-151.32  178
 19  \w   -137.00 -48.00   0.50    0.33    --  -70.00 -72.00 -95.61  178
 20  \w   -137.00 -48.00   0.50    0.33    --  -70.00 -72.00   9.04  178
 21  \w   -137.00 -48.00   0.50    0.33    --  -70.00 -72.00 -15.70  178
 22  \w   -138.00 -50.00   0.50    0.33    --  -70.00 -68.00  60.84  176
 23  \w   -137.00 -48.00   0.50    0.33    --  -70.00 -73.00 118.62  178
 24  \w   -137.00 -48.00   0.50    0.33    --  -70.00 -73.00 158.02  178
 25  \w   -137.00 -48.00   0.50    0.33    --  -70.00 -73.00 -43.95  178
 26  \w    -95.00  -9.00   0.50    0.33    --  -70.00 125.00-120.00  172
 27  \w   -141.00 -54.00   0.50    0.33    --  -70.00 -58.00-164.51  174
 28  \w   -137.00 -49.00   0.50    0.33    --  -70.00 -71.00  93.10  176
 29  \w   -139.00 -51.00   0.50    0.33    --  -70.00 -66.00  25.43  176
 30  \w    -94.00  -3.00   0.50    0.33    --  -70.00  77.00-180.00  182
 31  \w   -137.00 -48.00   0.50    0.33    --  -70.00 -73.00-171.41  178
 32  \w   -137.00 -48.00   0.50    0.33    --  -70.00 -73.00 -58.10  178
 33  \w     60.00 148.00   0.50    0.10    --   78.00  64.00 -81.92  176
 34  \w     74.00 161.00   0.50    0.33    --   90.00  59.00  49.71  174
 35  \w     86.00 177.00   0.50    0.33    --  110.00  77.00-180.00  182
 36  \w     86.00 177.00   0.50    0.33    --  110.00  77.00 -60.00  182
 37  \w     44.00 134.00   0.50    0.33    --  110.00 -77.00-150.00  180
 38  \w     94.00 178.00   0.50    0.33    --  110.00  57.00 -60.00  168
 39  \w     94.00 178.00   0.50    0.33    --  110.00  57.00  90.00  168
 40  \w     86.00 177.00   0.50    0.33    --  110.00  77.00  90.00  182
 41  \w     86.00 177.00   0.50    0.33    --  110.00  77.00 -90.00  182
 42  \w     98.00 178.00   0.50    0.33    --  110.00  38.00-120.00  160
 43  \w     86.00 177.00   0.50    0.33    --  110.00  77.00-120.00  182
 44  \w     40.00 110.00   0.50    0.33    --  110.00 -99.00   0.00  140
 45  \w     86.00 177.00   0.50    0.33    --  110.00  77.00 -30.00  182
 46  \w     94.00 178.00   0.50    0.33    --  110.00  57.00   0.00  168
 47  \w     98.00 178.00   0.50    0.33    --  110.00  38.00  30.00  160
 48  \w     40.00 110.00   0.50    0.33    --  110.00 -99.00  60.00  140
 49  \w     39.00 122.00   0.50    0.33    --  110.00-125.00-180.00  166
 50  \w     40.00 110.00   0.50    0.33    --  110.00 -99.00  30.00  140
 51  \w     40.00 110.00   0.50    0.33    --  110.00 -99.00 -90.00  140
 52  \w     86.00 177.00   0.50    0.33    --  110.00  77.00 150.00  182
 53  \w     86.00 177.00   0.50    0.33    --  110.00  77.00  30.00  182
 54  \w     86.00 177.00   0.50    0.33    --  110.00  77.00 120.00  182
 55  \w     86.00 177.00   0.50    0.33    --  110.00  77.00-150.00  182
 56  \w     98.00 178.00   0.50    0.33    --  110.00  38.00 120.00  160
 57  \w     94.00 178.00   0.50    0.33    --  110.00  57.00 -90.00  168
 58  \w     98.00 178.00   0.50    0.33    --  110.00  38.00-150.00  160
 59  \w     40.00 110.00   0.50    0.33    --  110.00 -99.00-150.00  140
 60  \w     94.00 178.00   0.50    0.33    --  110.00  57.00  60.00  168
 61  \w    140.00 174.00   0.50    0.33    --  110.00  77.00  60.00   68
 62  \w     86.00 136.00   0.50    0.33    --  110.00  77.00  60.00  100
 63  \w     62.00  94.00   0.50    0.33    --  110.00-125.00 150.00   64
;
_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      0.1026222000
_diffrn_orient_matrix_UB_12      -0.1379952000
_diffrn_orient_matrix_UB_13      0.0080241000
_diffrn_orient_matrix_UB_21      -0.0148209000
_diffrn_orient_matrix_UB_22      -0.0121669000
_diffrn_orient_matrix_UB_23      -0.1003778000
_diffrn_orient_matrix_UB_31      0.1021150000
_diffrn_orient_matrix_UB_32      0.1370043000
_diffrn_orient_matrix_UB_33      -0.0006991000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0359
_diffrn_reflns_av_unetI/netI     0.0179
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            49250
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.579
_diffrn_reflns_theta_min         2.888
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.580
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.661
_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    1.129
_exptl_crystal_description       plate
_exptl_crystal_F_000             480
_exptl_crystal_size_max          0.232
_exptl_crystal_size_mid          0.157
_exptl_crystal_size_min          0.066
_refine_diff_density_max         0.168
_refine_diff_density_min         -0.164
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 2324 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     301
_refine_ls_number_reflns         5561
_refine_ls_number_restraints     5
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0334
_refine_ls_R_factor_gt           0.0320
_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^)+(0.0440P)^2^+0.1457P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0847
_refine_ls_wR_factor_ref         0.0858
_reflns_Friedel_coverage         0.848
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.982
_reflns_number_gt                5315
_reflns_number_total             5561
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b05830_si_007.cif
_cod_data_source_block           ca020418_1_1
_cod_database_code               4128621
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C14H20O2
_reflns_odcompleteness_completeness 100.00
_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
 At 1.5 times of:
  All O(H) groups
2. Restrained distances
 O1-H1 = O1A-H1AA
 0.93 with sigma of 0.02
 O2A-H2AA = O2-H2
 0.93 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C3(H3), C10(H10), C3A(H3A), C10A(H10A)
3.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C11A(H11C,
 H11D), C12A(H12C,H12D), C13A(H13C,H13D), C14A(H14C,H14D)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2A), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C2A(H2AB), C5A(H5A),
 C6A(H6A), C7A(H7A), C8A(H8A), C9A(H9A)
3.d X=CH2 refined with riding coordinates:
 C1(H1A,H1B), C1A(H1AB,H1AC)
;
_shelx_res_checksum              55087
_shelx_hkl_checksum              50675
_olex2_date_sample_data_collection 2018-04-03
_olex2_date_sample_submission    2018-04-03
_olex2_submission_original_sample_id ca020418_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 1.216
_oxdiff_exptl_absorpt_empirical_full_min 0.852