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_4128625
_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         'C18 H17 Cl N2 O4'
_chemical_formula_sum            'C18 H17 Cl N2 O4'
_chemical_formula_weight         360.78
_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     iterative
_audit_creation_date             2015-04-24
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.361(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.8468(14)
_cell_length_b                   8.0192(14)
_cell_length_c                   13.739(2)
_cell_measurement_reflns_used    1961
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      27.03
_cell_measurement_theta_min      2.61
_cell_volume                     860.7(2)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker Apex2 Duo (Mo)'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'focusing graphite'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0506
_diffrn_reflns_av_unetI/netI     0.0826
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_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            7352
_diffrn_reflns_point_group_measured_fraction_full 0.954
_diffrn_reflns_point_group_measured_fraction_max 0.929
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.554
_diffrn_reflns_theta_min         1.489
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.247
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5761
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0724 before and 0.0606 after correction.
The Ratio of minimum to maximum transmission is 0.7727.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.392
_exptl_crystal_description       plank
_exptl_crystal_F_000             376
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.178
_refine_diff_density_min         -0.195
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details
;
 Flack x determined using 1015 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.09(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.959
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     264
_refine_ls_number_reflns         3703
_refine_ls_number_restraints     324
_refine_ls_restrained_S_all      0.925
_refine_ls_R_factor_all          0.0640
_refine_ls_R_factor_gt           0.0388
_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^)+(0.0036P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0739
_refine_ls_wR_factor_ref         0.0816
_reflns_Friedel_coverage         0.743
_reflns_Friedel_fraction_full    0.900
_reflns_Friedel_fraction_max     0.853
_reflns_number_gt                2783
_reflns_number_total             3703
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b05830_si_008.cif
_cod_data_source_block           mo_ca190415_1_1_0m
_cod_original_cell_volume        860.8(3)
_cod_database_code               4128625
_shelxl_version_number           2014/6
_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
 N9-H9
 0.91 with sigma of 0.02
 Cl1A-C16 \\sim Cl1-C16
 with sigma of 0.02
 C18-C11 \\sim C18-C11A
 with sigma of 0.02
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C11) = Uanis(C11A)
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H16A)=Sof(Cl1A)=1-FVAR(1)
 Sof(Cl1)=Sof(H16)=FVAR(1)
 Sof(H18A)=Sof(C11A)=Sof(C15A)=Sof(H15A)=Sof(C24A)=Sof(H24A)=Sof(C25A)=
 Sof(H25A)=Sof(C23A)=Sof(H23A)=Sof(C20A)=Sof(H20A)=1-FVAR(2)
 Sof(C11)=Sof(C20)=Sof(H20)=Sof(C23)=Sof(H23)=Sof(C25)=Sof(H25)=Sof(C24)=
 Sof(H24)=Sof(C15)=Sof(H15)=Sof(H18)=FVAR(2)
7.a Ternary CH refined with riding coordinates:
 C16(H16), C16(H16A), C18(H18), C18(H18A)
7.b Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B)
7.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C10(H10), C20(H20), C23(H23), C25(H25), C24(H24), C15(H15), C14(H14),
 C17(H17), C19(H19), C15A(H15A), C24A(H24A), C25A(H25A), C23A(H23A), C20A(H20A)
7.d Fitted hexagon refined as free rotating group:
 C11(C20,C23,C25,C24,C15), C11A(C15A,C24A,C25A,C23A,C20A)
7.e X=CH2 refined with riding coordinates:
 C1(H1A,H1B)
;
_shelx_res_checksum              68890
_shelx_hkl_checksum              24870
_olex2_date_sample_data_collection 2015-04-22
_olex2_date_sample_submission    2015-04-21
_olex2_submission_original_sample_id ca190415_1_1
_olex2_submission_special_instructions 'No special instructions were received'