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_4128626
_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, C13 H14 N O'
_chemical_formula_sum            'C13 H14 Cl N O'
_chemical_formula_weight         235.70
_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             2018-07-02
_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                   6.2187(2)
_cell_length_b                   7.2638(2)
_cell_length_c                   27.5254(7)
_cell_measurement_reflns_used    11430
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      79.2390
_cell_measurement_theta_min      3.2140
_cell_volume                     1243.36(6)
_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 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     14.00  44.00   0.50    2.22    --   38.00  79.00 -83.29   60
  2  \w      5.00  31.00   0.50    2.22    --   34.00  89.00-164.60   52
  3  \w     36.00  63.00   0.50    2.22    --   58.00  73.00  -9.41   54
  4  \w     28.00  58.00   0.50    2.22    --   50.00  73.00  56.05   60
  5  \w     34.00  61.00   0.50    2.22    --   54.00  72.00 124.52   54
  6  \w     94.00 123.00   0.50    8.87    --  110.00  57.00 150.00   58
  7  \w    122.00 176.00   0.50    8.87    --  110.00  77.00 120.00  108
  8  \w    152.00 177.00   0.50    8.87    --  110.00  77.00  90.00   50
  9  \w    146.00 172.00   0.50    8.87    --  110.00  57.00  90.00   52
 10  \w    134.00 176.00   0.50    8.87    --  110.00  77.00 150.00   84
 11  \w    129.00 156.00   0.50    8.87    --  110.00  77.00   0.00   54
 12  \w    120.00 170.00   0.50    8.87    --  110.00  77.00 -60.00  100
 13  \w    125.00 173.00   0.50    8.87    --  110.00  77.00-120.00   96
 14  \w    122.00 171.00   0.50    8.87    --  110.00  77.00 -30.00   98
 15  \w     95.00 147.00   0.50    8.87    --  110.00  57.00-180.00  104
 16  \w     94.00 121.00   0.50    8.87    --  110.00  57.00-120.00   54
 17  \w     94.00 140.00   0.50    8.87    --  110.00  57.00 -90.00   92
 18  \w     99.00 129.00   0.50    8.87    --  110.00  38.00 -30.00   60
 19  \w     86.00 112.00   0.50    8.87    --  110.00  77.00   0.00   52
 20  \w     94.00 145.00   0.50    8.87    --  110.00  60.00  11.82  102
 21  \w     88.00 173.00   0.50    8.87    --  110.00  77.00 -90.00  170
 22  \w     86.00 173.00   0.50    8.87    --  110.00  77.00  60.00  174
 23  \w     94.00 127.00   0.50    8.87    --  110.00  57.00  90.00   66
 24  \w     99.00 126.00   0.50    8.87    --  110.00  38.00 150.00   54
 25  \w     87.00 113.00   0.50    8.87    --  110.00  77.00 120.00   52
 26  \w     86.00 139.00   0.50    8.87    --  110.00  77.00  90.00  106
 27  \w     87.00 159.00   0.50    8.87    --  110.00  77.00  30.00  144
 28  \w     86.00 114.00   0.50    8.87    --  110.00  77.00 -60.00   56
 29  \w     87.00 120.00   0.50    8.87    --  110.00  77.00-120.00   66
 30  \w     87.00 158.00   0.50    8.87    --  110.00  77.00-180.00  142
 31  \w     86.00 173.00   0.50    8.87    --  110.00  77.00-150.00  174
 32  \w     87.00 133.00   0.50    8.87    --  110.00  78.00  16.74   92
 33  \w     86.00 117.00   0.50    8.87    --  110.00  77.00 -30.00   62
 34  \w     87.00 127.00   0.50    8.87    --  110.00  77.00 150.00   80
 35  \w     44.00  80.00   0.50    8.87    --  110.00 -57.00  30.00   72
 36  \w    108.00 133.00   0.50    8.87    --  110.00 -77.00  90.00   50
 37  \w     53.00  91.00   0.50    8.87    --  110.00 -77.00  90.00   76
 38  \w     57.00 103.00   0.50    8.87    --  110.00-125.00  60.00   92
 39  \w     40.00 103.00   0.50    8.87    --  110.00 -99.00 -60.00  126
 40  \w     89.00 119.00   0.50    8.87    --  110.00-125.00 -90.00   60
 41  \w     97.00 122.00   0.50    8.87    --  110.00 -77.00-120.00   50
 42  \w     50.00  79.00   0.50    8.87    --  110.00 -77.00-120.00   58
 43  \w     46.00  83.00   0.50    8.87    --  110.00-125.00 -90.00   74
 44  \w     48.00  92.00   0.50    8.87    --  110.00 -99.00-180.00   88
 45  \w    -23.00  35.00   0.50    2.22    --   48.87 -38.00 -30.00  116
 46  \w     45.00 107.00   0.50    8.87    --  110.00 -99.00  60.00  124
 47  \w    -58.00 -33.00   0.50    2.22    --  -48.87 -57.00 120.00   50
 48  \w    -61.00 -32.00   0.50    2.22    --  -54.00 -73.00  35.68   58
 49  \w    -65.00 -36.00   0.50    2.22    --  -58.00 -73.00  97.61   58
 50  \w    -70.00 -45.00   0.50    8.87    --  -62.00 -70.00  17.36   50
 51  \w    -69.00 -36.00   0.50    2.22    --  -48.87 -19.00 -60.00   66
 52  \w    -68.00 -41.00   0.50    8.87    --  -62.00 -73.00 -90.99   54
 53  \w    -76.00 -50.00   0.50    8.87    --  -70.00 -67.00 -57.57   52
 54  \w    -78.00 -50.00   0.50    8.87    --  -70.00 -67.00 -78.31   56
 55  \w    -77.00 -51.00   0.50    8.87    --  -70.00 -64.00 -31.20   52
 56  \w    -79.00 -54.00   0.50    8.87    --  -70.00 -57.00 -60.00   50
 57  \w    -85.00 -51.00   0.50    8.87    --  -70.00 -66.00   2.94   68
 58  \w    -81.00 -51.00   0.50    8.87    --  -70.00 -67.00  48.31   60
 59  \w    -77.00 -51.00   0.50    8.87    --  -70.00 -65.00  77.75   52
 60  \w    -77.00 -49.00   0.50    8.87    --  -70.00 -70.00 133.86   56
 61  \w    -73.00 -48.00   0.50    8.87    --  -70.00 -72.00 151.56   50
 62  \w    -83.00 -41.00   0.50    2.22    --  -48.87 -19.00 150.00   84
 63  \w    -85.00 -35.00   0.50    2.22    --  -48.87 -38.00 120.00  100
 64  \w    -77.00 -52.00   0.50    8.87    --  -70.00 -62.00  57.63   50
 65  \w    -86.00 -49.00   0.50    8.87    --  -70.00 -71.00 111.59   74
 66  \w    -79.00 -54.00   0.50    8.87    --  -70.00 -58.00 170.93   50
 67  \w    -79.00 -54.00   0.50    8.87    --  -70.00 -57.00 150.00   50
 68  \w   -117.00 -92.00   0.50    2.22    --  -48.87 -57.00 120.00   50
 69  \w   -114.00 -89.00   0.50    2.22    --  -48.87 -19.00 150.00   50
 70  \w   -112.00 -86.00   0.50    8.87    --  -70.00 -67.00  48.31   52
 71  \w   -130.00-104.00   0.50    8.87    --  -62.00 -70.00  17.36   52
 72  \w   -112.00 -86.00   0.50    2.22    --  -48.87 -19.00 -60.00   52
 73  \w   -129.00 -87.00   0.50    8.87    --  -62.00 -73.00 -90.99   84
 74  \w    -89.00 -49.00   0.50    8.87    --  -70.00 -70.00-101.98   80
 75  \w    -87.00 -52.00   0.50    8.87    --  -70.00 -62.00-158.80   70
 76  \w    -85.00 -48.00   0.50    8.87    --  -70.00 -73.00-120.68   74
 77  \w   -135.00-104.00   0.50    8.87    --  -70.00 -70.00-101.98   62
 78  \w    -86.00  -3.00   0.50    8.87    --  -70.00  77.00 -90.00  166
 79  \w    -53.00 -28.00   0.50    2.22    --   14.00 156.00-149.97   50
 80  \w    -72.00 -20.00   0.50    8.87    --  -70.00 125.00  60.00  104
 81  \w   -139.00-112.00   0.50    8.87    --  -70.00 -58.00 170.93   54
 82  \w   -136.00-110.00   0.50    8.87    --  -70.00 -72.00 151.56   52
;
_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      -0.0399211000
_diffrn_orient_matrix_UB_12      0.2057497000
_diffrn_orient_matrix_UB_13      0.0101171000
_diffrn_orient_matrix_UB_21      -0.0175840000
_diffrn_orient_matrix_UB_22      0.0362588000
_diffrn_orient_matrix_UB_23      -0.0549875000
_diffrn_orient_matrix_UB_31      -0.2439383000
_diffrn_orient_matrix_UB_32      -0.0363486000
_diffrn_orient_matrix_UB_33      0.0023371000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0646
_diffrn_reflns_av_unetI/netI     0.0231
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            27420
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.247
_diffrn_reflns_theta_min         3.211
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.540
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.660
_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    1.259
_exptl_crystal_description       plate
_exptl_crystal_F_000             496
_exptl_crystal_size_max          0.172
_exptl_crystal_size_mid          0.087
_exptl_crystal_size_min          0.013
_refine_diff_density_max         0.669
_refine_diff_density_min         -0.462
_refine_diff_density_rms         0.081
_refine_ls_abs_structure_details
;
 Flack x determined using 844 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.038(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     171
_refine_ls_number_reflns         2678
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0729
_refine_ls_R_factor_gt           0.0667
_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^)+(0.1528P)^2^+0.1512P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2010
_refine_ls_wR_factor_ref         0.2104
_reflns_Friedel_coverage         0.673
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.975
_reflns_number_gt                2332
_reflns_number_total             2678
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b05830_si_003.cif
_cod_data_source_block           ca050618_3_1
_cod_database_code               4128626
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C13H13ClNO
_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 O(H) groups
2. Restrained distances
 H1A-H1B
 1.44 with sigma of 0.02
 N1-H1A = N1-H1B
 0.93 with sigma of 0.02
 O1-H1A
 -2 with sigma of 0.02
 C3-C2A \\sim C3-C2
 with sigma of 0.02
 C2-C1 \\sim C2A-C1A
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 C3, C2, C1A, C1, C2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(H3B)=Sof(C2A)=Sof(H2A)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=1-FVAR(1)
 Sof(H3A)=Sof(C2)=Sof(H2)=Sof(C1)=Sof(H1C)=Sof(H1D)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C3(H3A), C3(H3B)
5.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C10(H10), C5(H5), C7(H7), C13(H13), C8(H8), C9(H9), C2(H2), C2A(H2A)
5.c X=CH2 refined with riding coordinates:
 C1(H1C,H1D), C1A(H1AA,H1AB)
5.d Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              34943
_shelx_hkl_checksum              62645
_olex2_date_sample_data_collection 2018-07-29
_olex2_date_sample_submission    2018-07-28
_olex2_submission_original_sample_id ca050618_3_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 1.648
_oxdiff_exptl_absorpt_empirical_full_min 0.677