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_4128623
_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         'C22 H19 Br2 N O2'
_chemical_formula_sum            'C22 H19 Br2 N O2'
_chemical_formula_weight         489.20
_chemical_name_systematic
'2-bromo-3-(naphthalen-2-yl)pent-4-en-1-yl (4-bromophenyl)carbamate'
_space_group_crystal_system      tetragonal
_space_group_IT_number           76
_space_group_name_Hall           'P 4w'
_space_group_name_H-M_alt        'P 41'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-02-27
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.9521(2)
_cell_length_b                   17.9521(2)
_cell_length_c                   12.3975(3)
_cell_measurement_reflns_used    18813
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      78.6540
_cell_measurement_theta_min      3.4740
_cell_volume                     3995.44(12)
_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 1.000
_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    -83.00 -37.00   0.50    8.00    --  -49.12 -38.00 120.00   92
  2  \w   -115.00 -79.00   0.50    8.00    --  -49.12 -77.00 -30.00   72
  3  \w   -111.00 -80.00   0.50    8.00    --  -49.12 -77.00  60.00   62
  4  \w   -110.00 -83.00   0.50   18.00    --  -70.00 -77.00  30.00   54
  5  \w   -113.00 -82.00   0.50    8.00    --  -49.12 -77.00 120.00   62
  6  \w   -118.00 -92.00   0.50    8.00    --  -49.12 -38.00 120.00   52
  7  \w   -140.00 -91.00   0.50   18.00    --  -70.00-125.00 150.00   98
  8  \w   -138.00 -92.00   0.50   18.00    --  -70.00-125.00  60.00   92
  9  \w   -114.00 -80.00   0.50    8.00    --  -49.12 -77.00 -60.00   68
 10  \w   -123.00 -39.00   0.50    8.00    --  -49.12 -38.00-150.00  168
 11  \w   -101.00 -47.00   0.50    8.00    --  -49.12-178.00-120.00  108
 12  \w   -135.00-109.00   0.50   18.00    --  -70.00 -77.00 -90.00   52
 13  \w   -136.00 -81.00   0.50   18.00    --  -70.00 -77.00-180.00  110
 14  \w    -94.00 -50.00   0.50    8.00    --  -49.12 122.00-117.00   88
 15  \w    -91.00  -6.00   0.50   18.00    --  -70.00  77.00 120.00  170
 16  \w     38.00  72.00   0.50   18.00    --  110.00 -57.00-180.00   68
 17  \w     94.00 119.00   0.50   18.00    --  110.00 -19.00-180.00   50
 18  \w     94.00 119.00   0.50   18.00    --  110.00 -19.00-120.00   50
 19  \w     94.00 120.00   0.50   18.00    --  110.00 -19.00 -60.00   52
 20  \w     97.00 123.00   0.50   18.00    --  110.00 -19.00   0.00   52
 21  \w    122.00 171.00   0.50   18.00    --  110.00  19.00  30.00   98
 22  \w    146.00 176.00   0.50   18.00    --  110.00  77.00 -60.00   60
 23  \w    153.00 178.00   0.50   18.00    --  110.00  57.00 -90.00   50
 24  \w    146.00 172.00   0.50   18.00    --  110.00  77.00-150.00   52
 25  \w    138.00 176.00   0.50   18.00    --  110.00  77.00-180.00   76
 26  \w     99.00 174.00   0.50   18.00    --  110.00  57.00-120.00  150
 27  \w    105.00 131.00   0.50   18.00    --  110.00  57.00 -90.00   52
 28  \w    100.00 143.00   0.50   18.00    --  110.00  38.00 -90.00   86
 29  \w     90.00 121.00   0.50   18.00    --  110.00  77.00 -60.00   62
 30  \w     94.00 120.00   0.50   18.00    --  110.00  77.00-150.00   52
 31  \w     92.00 120.00   0.50   18.00    --  110.00  77.00-180.00   56
 32  \w     38.00  83.00   0.50   18.00    --  110.00 -57.00 -30.00   90
 33  \w    101.00 134.00   0.50   18.00    --  110.00 -77.00 -60.00   66
 34  \w     95.00 121.00   0.50   18.00    --  110.00 -19.00  30.00   52
 35  \w     95.00 122.00   0.50   18.00    --  110.00 -19.00  60.00   54
 36  \w    100.00 129.00   0.50   18.00    --  110.00 -77.00 150.00   58
 37  \w     62.00 102.00   0.50   18.00    --  110.00 -99.00   0.00   80
 38  \w     59.00  86.00   0.50   18.00    --  110.00 -77.00 -60.00   54
 39  \w     44.00  83.00   0.50   18.00    --  110.00 -57.00 -90.00   78
 40  \w     40.00 110.00   0.50   18.00    --  110.00 -99.00 -60.00  140
 41  \w     57.00  83.00   0.50   18.00    --  110.00 -99.00-180.00   52
 42  \w     41.00 110.00   0.50   18.00    --  110.00 -99.00-150.00  138
 43  \w     39.00  84.00   0.50   18.00    --  110.00 -57.00  90.00   90
 44  \w     41.00 109.00   0.50   18.00    --  110.00 -99.00 120.00  136
 45  \w     57.00 119.00   0.50   18.00    --  110.00-125.00 120.00  124
 46  \w    109.00 163.00   0.50   18.00    --  110.00  77.00 120.00  108
;
_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      0.0796023000
_diffrn_orient_matrix_UB_12      0.0315916000
_diffrn_orient_matrix_UB_13      0.0074071000
_diffrn_orient_matrix_UB_21      0.0308339000
_diffrn_orient_matrix_UB_22      -0.0794040000
_diffrn_orient_matrix_UB_23      0.0151842000
_diffrn_orient_matrix_UB_31      0.0086584000
_diffrn_orient_matrix_UB_32      -0.0079212000
_diffrn_orient_matrix_UB_33      -0.1231140000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0670
_diffrn_reflns_av_unetI/netI     0.0384
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            52363
_diffrn_reflns_point_group_measured_fraction_full 0.919
_diffrn_reflns_point_group_measured_fraction_max 0.913
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.089
_diffrn_reflns_theta_min         3.482
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.280
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.579
_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    1.627
_exptl_crystal_description       needle
_exptl_crystal_F_000             1952
_exptl_crystal_size_max          0.158
_exptl_crystal_size_mid          0.013
_exptl_crystal_size_min          0.009
_refine_diff_density_max         2.556
_refine_diff_density_min         -1.144
_refine_diff_density_rms         0.138
_refine_ls_abs_structure_details
;
 Flack x determined using 2365 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.041(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     493
_refine_ls_number_reflns         7176
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0646
_refine_ls_R_factor_gt           0.0569
_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^)+(0.1132P)^2^+0.1346P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1482
_refine_ls_wR_factor_ref         0.1535
_reflns_Friedel_coverage         0.740
_reflns_Friedel_fraction_full    0.829
_reflns_Friedel_fraction_max     0.816
_reflns_number_gt                6325
_reflns_number_total             7176
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b05830_si_004.cif
_cod_data_source_block           ca260218_1_1
_cod_original_cell_volume        3995.44(13)
_cod_database_code               4128623
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C22 H19 Br2 N O2'
_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
2. Restrained distances
 N1B-H1B = N1A-H1A
 0.93 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C9A(H9A), C10A(H10A), C9B(H9B), C10B(H10B)
3.b Secondary CH2 refined with riding coordinates:
 C8A(H8AA,H8AB), C8B(H8BA,H8BB)
3.c Aromatic/amide H refined with riding coordinates:
 C2A(H2A), C3A(H3A), C5A(H5A), C6A(H6A), C11A(H11A), C14A(H14A), C16A(H16A),
 C17A(H17A), C18A(H18A), C19A(H19A), C21A(H21A), C22A(H22A), C2B(H2B), C3B(H3B),
  C5B(H5B), C6B(H6B), C11B(H11B), C14B(H14B), C16B(H16B), C17B(H17B),
 C18B(H18B), C19B(H19B), C21B(H21B), C22B(H22B)
3.d X=CH2 refined with riding coordinates:
 C12A(H12A,H12B), C12B(H12C,H12D)
;
_shelx_res_checksum              26591
_shelx_hkl_checksum              75374
_olex2_date_sample_data_collection 2018-02-26
_olex2_date_sample_submission    2018-02-26
_olex2_submission_original_sample_id ca260218_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 1.646
_oxdiff_exptl_absorpt_empirical_full_min 0.588