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_4128624
_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 N4'
_chemical_formula_sum            'C15 H14 N4'
_chemical_formula_weight         250.30
_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             2018-11-13
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.2759(7)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.55961(5)
_cell_length_b                   8.22570(5)
_cell_length_c                   13.54910(8)
_cell_measurement_reflns_used    19588
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      79.2420
_cell_measurement_theta_min      3.2460
_cell_volume                     619.470(8)
_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    '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 0.991
_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     29.00 121.00   0.50    0.10    --   54.00  81.00-144.19  184
  2  \w     32.00 125.00   0.50    0.10    --   58.00  83.00 -25.33  186
  3  \w     91.00 178.00   0.50    0.10    --  110.00 125.00 150.00  174
  4  \w     65.00 157.00   0.50    0.10    --   90.00  81.00  36.11  184
  5  \w     38.00 128.00   0.50    0.10    --   62.00  79.00-112.09  180
  6  \w     86.00 177.00   0.50    0.10    --  110.00  77.00-180.00  182
  7  \w     86.00 177.00   0.50    0.10    --  110.00  77.00-120.00  182
  8  \w     86.00 177.00   0.50    0.10    --  110.00  77.00 -30.00  182
  9  \w    -95.00  -9.00   0.50    0.10    --  -70.00 125.00 120.00  172
 10  \w     24.00 117.00   0.50    0.10    --   50.00  83.00  27.88  186
 11  \w     45.00 137.00   0.50    0.10    --   70.00  80.00  74.36  184
 12  \w     47.00 136.00   0.50    0.10    --   70.00  75.00 -47.22  178
 13  \w     72.00 160.00   0.50    0.10    --   86.00  49.00 -73.61  176
 14  \w     57.00 145.00   0.50    0.10    --   74.00  61.00 -87.38  176
 15  \w     80.00 168.00   0.50    0.10    --   94.00  49.00   1.89  176
 16  \w     98.00 178.00   0.50    0.10    --  110.00  38.00 -60.00  160
 17  \w     86.00 177.00   0.50    0.10    --  110.00  77.00 -90.00  182
 18  \w     86.00 177.00   0.50    0.10    --  110.00  77.00 -60.00  182
 19  \w     86.00 177.00   0.50    0.10    --  110.00  77.00 120.00  182
 20  \w     86.00 177.00   0.50    0.10    --  110.00  77.00  90.00  182
 21  \w     94.00 178.00   0.50    0.10    --  110.00  57.00  90.00  168
 22  \w     86.00 177.00   0.50    0.10    --  110.00  77.00 150.00  182
 23  \w     98.00 178.00   0.50    0.10    --  110.00  38.00  30.00  160
 24  \w     98.00 178.00   0.50    0.10    --  110.00  38.00 -90.00  160
 25  \w     98.00 178.00   0.50    0.10    --  110.00  38.00-120.00  160
 26  \w     86.00 177.00   0.50    0.10    --  110.00  77.00-150.00  182
 27  \w     94.00 178.00   0.50    0.10    --  110.00  57.00 150.00  168
 28  \w     86.00 177.00   0.50    0.10    --  110.00  77.00  60.00  182
 29  \w     26.00 116.00   0.50    0.10    --   49.37  77.00 -60.00  180
 30  \w     37.00 125.00   0.50    0.10    --   49.37  19.00-120.00  176
 31  \w     37.00 125.00   0.50    0.10    --   49.37  38.00 -30.00  176
 32  \w     26.00 116.00   0.50    0.10    --   49.37  77.00 120.00  180
 33  \w     37.00 125.00   0.50    0.10    --   49.37  38.00 -90.00  176
 34  \w     34.00 121.00   0.50    0.10    --   49.37  57.00 120.00  174
 35  \w     26.00 116.00   0.50    0.10    --   49.37  77.00-180.00  180
 36  \w     40.00 110.00   0.50    0.10    --  110.00 -99.00-120.00  140
 37  \w     40.00 110.00   0.50    0.10    --  110.00 -99.00 -60.00  140
 38  \w     39.00 122.00   0.50    0.10    --  110.00-125.00   0.00  166
 39  \w     40.00 110.00   0.50    0.10    --  110.00 -99.00 120.00  140
 40  \w     40.00 110.00   0.50    0.10    --  110.00 -99.00  90.00  140
 41  \w     57.00 122.00   0.50    0.10    --   49.37-178.00  60.00  130
 42  \w     44.00 134.00   0.50    0.10    --  110.00 -77.00 150.00  180
 43  \w     38.00  84.00   0.50    0.10    --  110.00 -57.00-150.00   92
 44  \w    -16.00  73.00   0.50    0.10    --   49.37 -77.00  60.00  178
 45  \w   -116.00 -26.00   0.50    0.10    --  -49.37 -77.00  30.00  180
 46  \w   -121.00 -34.00   0.50    0.10    --  -49.37 -57.00 120.00  174
 47  \w   -125.00 -36.00   0.50    0.10    --  -49.37 -38.00 150.00  178
 48  \w   -142.00 -54.00   0.50    0.10    --  -70.00 -57.00 120.00  176
 49  \w   -137.00 -46.00   0.50    0.10    --  -70.00 -77.00  90.00  182
 50  \w   -136.00 -47.00   0.50    0.10    --  -70.00 -74.00-177.93  178
 51  \w   -137.00 -46.00   0.50    0.10    --  -70.00 -77.00  30.00  182
 52  \w   -137.00 -46.00   0.50    0.10    --  -70.00 -77.00 -60.00  182
 53  \w   -137.00 -46.00   0.50    0.10    --  -70.00 -77.00  60.00  182
 54  \w   -136.00 -45.00   0.50    0.10    --  -70.00 -79.00-178.47  182
 55  \w   -137.00 -46.00   0.50    0.10    --  -70.00 -77.00 -30.00  182
 56  \w   -140.00 -51.00   0.50    0.10    --  -70.00 -64.00-162.44  178
 57  \w   -137.00 -46.00   0.50    0.10    --  -70.00 -77.00   0.00  182
 58  \w   -128.00 -37.00   0.50    0.10    --  -62.00 -80.00-123.49  182
;
_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      0.0075776000
_diffrn_orient_matrix_UB_12      0.0010361000
_diffrn_orient_matrix_UB_13      -0.1135383000
_diffrn_orient_matrix_UB_21      0.1003005000
_diffrn_orient_matrix_UB_22      0.1745877000
_diffrn_orient_matrix_UB_23      0.0026094000
_diffrn_orient_matrix_UB_31      0.2583780000
_diffrn_orient_matrix_UB_32      -0.0678213000
_diffrn_orient_matrix_UB_33      0.0050761000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0383
_diffrn_reflns_av_unetI/netI     0.0183
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            23694
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.764
_diffrn_reflns_theta_min         3.263
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.662
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.743
_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    1.342
_exptl_crystal_description       block
_exptl_crystal_F_000             264
_exptl_crystal_size_max          0.171
_exptl_crystal_size_mid          0.132
_exptl_crystal_size_min          0.046
_refine_diff_density_max         0.123
_refine_diff_density_min         -0.192
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 1161 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.13(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     175
_refine_ls_number_reflns         2640
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0298
_refine_ls_R_factor_gt           0.0293
_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^)+(0.0379P)^2^+0.1080P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0711
_refine_ls_wR_factor_ref         0.0717
_reflns_Friedel_coverage         0.845
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.966
_reflns_number_gt                2586
_reflns_number_total             2640
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b05830_si_006.cif
_cod_data_source_block           ca121118_1_1
_cod_original_cell_volume        619.470(7)
_cod_database_code               4128624
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C15H14N4
_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, All N(H) groups
2. Restrained distances
 N2-H2
 0.93 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C10(H10)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2A), C4(H4), C6(H6), C7(H7), C8(H8), C9(H9), C11(H11), C12(H12), C13(H13),
  C15(H15)
3.c X=CH2 refined with riding coordinates:
 C14(H14A,H14B)
;
_shelx_res_checksum              53687
_shelx_hkl_checksum              13835
_olex2_date_sample_data_collection 2018-11-12
_olex2_date_sample_submission    2018-11-12
_olex2_submission_original_sample_id ca121118_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 1.236
_oxdiff_exptl_absorpt_empirical_full_min 0.814