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_4128627
_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         'C15 H14 Cl2 O'
_chemical_formula_sum            'C15 H14 Cl2 O'
_chemical_formula_weight         281.16
_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             2018-03-08
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                83.978(6)
_cell_angle_beta                 88.299(7)
_cell_angle_gamma                88.260(6)
_cell_formula_units_Z            2
_cell_length_a                   5.8128(4)
_cell_length_b                   8.5698(6)
_cell_length_c                   13.4075(11)
_cell_measurement_reflns_used    1668
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      53.7360
_cell_measurement_theta_min      5.1970
_cell_volume                     663.66(9)
_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 0.978
_diffrn_measured_fraction_theta_max 0.978
_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    -14.00  74.00   0.50    3.50    --   -1.09  38.00 -90.00  176
  2  \w     59.00 127.00   0.50    3.50    --   56.14 178.00  30.00  136
  3  \w    -69.00  -3.00   0.50    3.50    --  -58.32  19.00-120.00  132
  4  \w    -82.00   8.00   0.50    3.50    --  -58.32  77.00 -90.00  180
  5  \w    -82.00   8.00   0.50    3.50    --  -58.32  77.00-150.00  180
  6  \w    -82.00   8.00   0.50    3.50    --  -58.32  77.00  60.00  180
  7  \w    -82.00   8.00   0.50    3.50    --  -58.32  77.00 120.00  180
  8  \w   -120.00 -64.00   0.50    3.50    --  -58.32 -57.00  30.00  112
  9  \w   -130.00 -43.00   0.50    3.50    --  -58.32 -57.00  90.00  174
 10  \w   -128.00 -84.00   0.50    3.50    --  -58.32 -99.00 150.00   88
 11  \w     40.00 115.00   0.50    3.50    --   56.14-143.00  46.00  150
 12  \w     32.00 106.00   0.50    3.50    --   56.14-127.00-144.00  148
 13  \w   -128.00 -84.00   0.50    3.50    --  -58.32 -99.00-180.00   88
;
_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      -0.1629869000
_diffrn_orient_matrix_UB_12      0.1397439000
_diffrn_orient_matrix_UB_13      -0.0331086000
_diffrn_orient_matrix_UB_21      0.0691486000
_diffrn_orient_matrix_UB_22      -0.0147355000
_diffrn_orient_matrix_UB_23      -0.1105025000
_diffrn_orient_matrix_UB_31      -0.1975083000
_diffrn_orient_matrix_UB_32      -0.1138188000
_diffrn_orient_matrix_UB_33      -0.0072271000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0530
_diffrn_reflns_av_unetI/netI     0.0696
_diffrn_reflns_Laue_measured_fraction_full 0.978
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            4212
_diffrn_reflns_point_group_measured_fraction_full 0.659
_diffrn_reflns_point_group_measured_fraction_max 0.659
_diffrn_reflns_theta_full        54.071
_diffrn_reflns_theta_max         54.071
_diffrn_reflns_theta_min         3.316
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.262
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.613
_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    1.407
_exptl_crystal_description       plate
_exptl_crystal_F_000             292
_exptl_crystal_size_max          0.135
_exptl_crystal_size_mid          0.057
_exptl_crystal_size_min          0.011
_refine_diff_density_max         0.675
_refine_diff_density_min         -0.432
_refine_diff_density_rms         0.100
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   -0.02(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     327
_refine_ls_number_reflns         2102
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0802
_refine_ls_R_factor_gt           0.0712
_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^)+(0.1407P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1782
_refine_ls_wR_factor_ref         0.1845
_reflns_Friedel_coverage         0.348
_reflns_Friedel_fraction_full    0.341
_reflns_Friedel_fraction_max     0.341
_reflns_number_gt                1806
_reflns_number_total             2102
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b05830_si_005.cif
_cod_data_source_block           ca060318_1_1
_cod_database_code               4128627
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C15H14Cl2O
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     50.38
_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.a Ternary CH refined with riding coordinates:
 C3B(H3B), C3A(H3A)
2.b Secondary CH2 refined with riding coordinates:
 C1B(H1BA,H1BB), C1A(H1AA,H1AB)
2.c Aromatic/amide H refined with riding coordinates:
 C15B(H15B), C8A(H8A), C4B(H4B), C10A(H10A), C15A(H15A), C7B(H7B), C7A(H7A),
 C13B(H13B), C8B(H8B), C13A(H13A), C11B(H11B), C4A(H4A), C11A(H11A), C10B(H10B),
  C12B(H12B), C12A(H12A)
2.d X=CH2 refined with riding coordinates:
 C5A(H5AA,H5AB), C5B(H5BA,H5BB)
2.e Idealised tetrahedral OH refined as rotating group:
 O1A(H1A), O1B(H1B)
;
_shelx_res_checksum              29875
_shelx_hkl_checksum              437
_olex2_date_sample_data_collection 2018-03-07
_olex2_date_sample_submission    2018-03-05
_olex2_submission_original_sample_id ca060318_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 1.707
_oxdiff_exptl_absorpt_empirical_full_min 0.651