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_4128622
_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         'Cl, C14 H16 N'
_chemical_formula_sum            'C14 H16 Cl N'
_chemical_formula_weight         233.73
_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             2018-07-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.95930(10)
_cell_length_b                   7.46620(10)
_cell_length_c                   24.7555(2)
_cell_measurement_reflns_used    23506
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      79.3410
_cell_measurement_theta_min      3.5600
_cell_volume                     1286.28(3)
_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 1.000
_diffrn_measured_fraction_theta_max 0.994
_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   -100.00 -70.00   0.50    0.12    --  -70.00 134.00  36.00   60
  2  \w    -67.00 -15.00   0.50    0.12    --  -70.00 134.00  36.00  104
  3  \w    -94.00 -10.00   0.50    0.12    --  -70.00 125.00 -90.00  168
  4  \w     32.00  60.00   0.50    0.10    --   58.00  82.00  74.32   56
  5  \w     86.00 130.00   0.50    0.12    --  110.00  77.00  90.00   88
  6  \w    133.00 177.00   0.50    0.12    --  110.00  77.00  90.00   88
  7  \w     98.00 136.00   0.50    0.12    --  110.00  57.00  60.00   76
  8  \w     97.00 153.00   0.50    0.12    --  110.00  57.00-120.00  112
  9  \w     96.00 123.00   0.50    0.12    --  110.00  57.00-150.00   54
 10  \w     96.00 122.00   0.50    0.12    --  110.00  57.00-180.00   52
 11  \w     98.00 124.00   0.50    0.12    --  110.00  38.00  60.00   52
 12  \w     59.00  98.00   0.50    0.10    --   78.00  67.00 -29.15   78
 13  \w     70.00 111.00   0.50    0.12    --   94.00  78.00-102.02   82
 14  \w     55.00  81.00   0.50    0.10    --   74.00  70.00-165.88   52
 15  \w    108.00 142.00   0.50    0.10    --   74.00  70.00-165.88   68
 16  \w    116.00 159.00   0.50    0.12    --   94.00  78.00-102.02   86
 17  \w    138.00 166.00   0.50    0.12    --  110.00  77.00 -90.00   56
 18  \w     85.00 171.00   0.50    0.12    --  106.00  72.00 -49.42  172
 19  \w     87.00 128.00   0.50    0.12    --  110.00  77.00   0.00   82
 20  \w    132.00 173.00   0.50    0.12    --  110.00  77.00  60.00   82
 21  \w     94.00 129.00   0.50    0.12    --  110.00  57.00   0.00   70
 22  \w     86.00 112.00   0.50    0.12    --  110.00  77.00  60.00   52
 23  \w     86.00 175.00   0.50    0.12    --  110.00  77.00 -30.00  178
 24  \w     86.00 112.00   0.50    0.12    --  110.00  77.00 -90.00   52
 25  \w     86.00 125.00   0.50    0.12    --  110.00  77.00-180.00   78
 26  \w    128.00 174.00   0.50    0.12    --  110.00  77.00-180.00   92
 27  \w    132.00 177.00   0.50    0.12    --  110.00  77.00   0.00   90
 28  \w    138.00 177.00   0.50    0.12    --  110.00  77.00  30.00   78
 29  \w     86.00 162.00   0.50    0.12    --  110.00  77.00 150.00  152
 30  \w     94.00 128.00   0.50    0.12    --  110.00  57.00 120.00   68
 31  \w     86.00 126.00   0.50    0.12    --  110.00  77.00  30.00   80
 32  \w     95.00 122.00   0.50    0.12    --  110.00  57.00  90.00   54
 33  \w     86.00 170.00   0.50    0.12    --  110.00  77.00 120.00  168
 34  \w    111.00 136.00   0.50    0.12    --  110.00  38.00  30.00   50
 35  \w     94.00 139.00   0.50    0.12    --  110.00  57.00 -60.00   90
 36  \w    124.00 176.00   0.50    0.12    --  110.00  77.00-150.00  104
 37  \w     88.00 113.00   0.50    0.12    --  110.00  77.00-150.00   50
 38  \w     26.00  56.00   0.50    0.10    --   49.37  77.00-150.00   60
 39  \w     28.00  53.00   0.50    0.10    --   49.37  77.00 -30.00   50
 40  \w     33.00  59.00   0.50    0.10    --   49.37  77.00  30.00   52
 41  \w     34.00  60.00   0.50    0.10    --   49.37  57.00  30.00   52
 42  \w     28.00  64.00   0.50    0.10    --   49.37  77.00 120.00   72
 43  \w     34.00  66.00   0.50    0.10    --   49.37  57.00  90.00   64
 44  \w     84.00 110.00   0.50    0.12    --  110.00 -99.00 -30.00   52
 45  \w     63.00 121.00   0.50    0.12    --  110.00-125.00-120.00  116
 46  \w     44.00  76.00   0.50    0.12    --  110.00 -99.00  30.00   64
 47  \w     52.00  78.00   0.50    0.12    --  110.00 -99.00 -30.00   52
 48  \w     65.00 106.00   0.50    0.12    --  110.00 -99.00  60.00   82
 49  \w     49.00  76.00   0.50    0.12    --  110.00-125.00 150.00   54
 50  \w     94.00 122.00   0.50    0.12    --  110.00-125.00 150.00   56
 51  \w     41.00  99.00   0.50    0.12    --  110.00 -99.00 150.00  116
 52  \w     42.00  72.00   0.50    0.12    --  110.00 -57.00 120.00   60
 53  \w     52.00 123.00   0.50    0.12    --  110.00 -77.00-120.00  142
 54  \w    -90.00 -39.00   0.50    0.10    --  -49.37 -38.00  30.00  102
 55  \w   -118.00 -87.00   0.50    0.10    --  -49.37 -38.00 -30.00   62
 56  \w    -84.00 -37.00   0.50    0.10    --  -49.37 -38.00 -30.00   94
 57  \w    -79.00 -38.00   0.50    0.10    --  -49.37 -57.00 -90.00   82
 58  \w    -61.00 -26.00   0.50    0.10    --  -49.37 -77.00-120.00   70
 59  \w    -68.00 -37.00   0.50    0.10    --  -49.37 -38.00-180.00   62
 60  \w   -112.00 -83.00   0.50    0.10    --  -49.37 -38.00-180.00   58
 61  \w   -111.00 -86.00   0.50    0.10    --  -49.37 -77.00-120.00   50
 62  \w    -76.00 -34.00   0.50    0.10    --  -49.37 -57.00 -60.00   84
 63  \w    -73.00 -47.00   0.50    0.12    --  -70.00 -77.00-120.00   52
 64  \w   -133.00-108.00   0.50    0.12    --  -70.00 -71.00-118.07   50
 65  \w   -136.00-109.00   0.50    0.12    --  -70.00 -77.00-150.00   54
 66  \w    -71.00 -46.00   0.50    0.12    --  -70.00 -77.00 -87.78   50
 67  \w    -76.00 -49.00   0.50    0.12    --  -70.00 -71.00   9.47   54
 68  \w    -71.00 -46.00   0.50    0.12    --  -70.00 -80.00  52.03   50
 69  \w    -84.00 -55.00   0.50    0.12    --  -70.00 -71.00  86.87   58
 70  \w    -72.00 -46.00   0.50    0.12    --  -70.00 -77.00 150.00   52
 71  \w    -82.00 -53.00   0.50    0.12    --  -70.00 -61.00  91.30   58
 72  \w    -79.00 -54.00   0.50    0.12    --  -70.00 -57.00  30.00   50
 73  \w    -77.00 -51.00   0.50    0.12    --  -70.00 -71.00-118.07   52
 74  \w    -72.00 -47.00   0.50    0.12    --  -70.00 -77.00-150.00   50
 75  \w    -74.00 -47.00   0.50    0.12    --  -70.00 -74.00-175.08   54
 76  \w    -71.00 -46.00   0.50    0.12    --  -70.00 -77.00 -60.00   50
 77  \w    -59.00 -32.00   0.50    0.10    --  -58.00 -82.00 111.21   54
 78  \w    -75.00 -44.00   0.50    0.12    --  -70.00 -83.00 119.94   62
 79  \w    -75.00 -43.00   0.50    0.12    --  -70.00 -83.00   1.48   64
 80  \w   -135.00-110.00   0.50    0.12    --  -70.00 -83.00 119.94   50
 81  \w   -117.00 -48.00   0.50    0.10    --  -49.37-178.00  90.00  138
;
_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      -0.0012741000
_diffrn_orient_matrix_UB_12      0.0122189000
_diffrn_orient_matrix_UB_13      0.0621165000
_diffrn_orient_matrix_UB_21      0.0541556000
_diffrn_orient_matrix_UB_22      -0.1997265000
_diffrn_orient_matrix_UB_23      0.0036578000
_diffrn_orient_matrix_UB_31      0.2146242000
_diffrn_orient_matrix_UB_32      0.0504476000
_diffrn_orient_matrix_UB_33      -0.0005939000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0453
_diffrn_reflns_av_unetI/netI     0.0190
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            29240
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.706
_diffrn_reflns_theta_min         3.571
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.389
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.638
_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    1.207
_exptl_crystal_description       plate
_exptl_crystal_F_000             496
_exptl_crystal_size_max          0.185
_exptl_crystal_size_mid          0.153
_exptl_crystal_size_min          0.056
_refine_diff_density_max         0.205
_refine_diff_density_min         -0.180
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 1095 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.002(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     152
_refine_ls_number_reflns         2762
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.080
_refine_ls_R_factor_all          0.0254
_refine_ls_R_factor_gt           0.0249
_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^)+(0.0338P)^2^+0.2998P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0658
_refine_ls_wR_factor_ref         0.0661
_reflns_Friedel_coverage         0.687
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.977
_reflns_number_gt                2711
_reflns_number_total             2762
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b05830_si_002.cif
_cod_data_source_block           ca020718_1_2
_cod_database_code               4128622
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C14H16NCl
_reflns_odcompleteness_completeness 99.93
_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,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-H1B = N1-H1A
 0.93 with sigma of 0.02
 H1B-H1A
 1.44 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C3(H3)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12), C14(H14)
3.c X=CH2 refined with riding coordinates:
 C1(H1C,H1D)
3.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C)
;
_shelx_res_checksum              12846
_shelx_hkl_checksum              92336
_olex2_date_sample_submission    2018-07-02
_olex2_submission_original_sample_id ca020718_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 1.194
_oxdiff_exptl_absorpt_empirical_full_min 0.821