Enantioselective Addition of Cyclic Ketones to Unactivated Alkenes Enabled by Amine/Pd(II) Cooperative Catalysis
Shen, Hong-Cheng; Zhang, Ling; Chen, Shu-Sen; Feng, Jiajie; Zhang, Bo-Wen; Zhang, Ying; Zhang, Xinhao; Wu, Yun-Dong; Gong, Liu-Zhu; ACS Catalysis 9 (2018) 791–; doi:10.1021/acscatal.8b04654

data_4515513
_publ_section_title
;
 Enantioselective Addition of Cyclic Ketones to Unactivated Alkenes
 Enabled by Amine/Pd(II) Cooperative Catalysis
;
_journal_issue                   2
_journal_name_full               'ACS Catalysis'
_journal_page_first              791
_journal_paper_doi               10.1021/acscatal.8b04654
_journal_volume                  9
_journal_year                    2018
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C25 H27 Br N2 O2'
_chemical_formula_sum            'C25 H27 Br N2 O2'
_chemical_formula_weight         467.39
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-07-12
_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            8
_cell_length_a                   9.0909(3)
_cell_length_b                   13.2501(4)
_cell_length_c                   36.0908(12)
_cell_measurement_reflns_used    9987
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      54.74
_cell_measurement_theta_min      4.264
_cell_volume                     4347.3(2)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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_temperature      173
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0644
_diffrn_reflns_av_unetI/netI     0.0479
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            46450
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         55.257
_diffrn_reflns_theta_min         3.091
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.888
_exptl_absorpt_correction_T_max  0.7508
_exptl_absorpt_correction_T_min  0.5858
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1423 before and 0.0881 after correction. The Ratio of minimum to maximum transmission is 0.7802. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.428
_exptl_crystal_description       block
_exptl_crystal_F_000             1936
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.395
_refine_diff_density_min         -0.540
_refine_diff_density_rms         0.064
_refine_ls_abs_structure_details
;
 Flack x determined using 2422 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.061(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     561
_refine_ls_number_reflns         8328
_refine_ls_number_restraints     62
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0646
_refine_ls_R_factor_gt           0.0468
_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^)+(0.0410P)^2^+2.6625P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1017
_refine_ls_wR_factor_ref         0.1124
_reflns_Friedel_coverage         0.773
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                6714
_reflns_number_total             8328
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b04654_si_003.cif
_cod_data_source_block           wmj18126_0m
_cod_database_code               4515513
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.911
_shelx_estimated_absorpt_t_min   0.765
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All O(H) groups
2. Restrained distances
 C12B-C13A = C12A-C13A = C11A-C12A = C11B-C12B = C11A-C10A = C11B-C10A = C13A-
 C14A
 1.53 with sigma of 0.02
 C13A-C12B
 1.53 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C13A \\sim C14A \\sim C11A \\sim C12A \\sim C11B \\sim C12B: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Fixed Sof: H13A(0.7) H13B(0.7) H13C(0.3) H13D(0.3) C11A(0.7) H11A(0.7)
 H11B(0.7) C12A(0.7) H12A(0.7) H12B(0.7) C11B(0.3) H11C(0.3) H11D(0.3)
 C12B(0.3) H12C(0.3) H12D(0.3)
5.a Ternary CH refined with riding coordinates:
 C14(H14), C15(H15), C18(H18), C14A(H14A), C15A(H15A), C18A(H18A)
5.b Secondary CH2 refined with riding coordinates:
 C11(H11E,H11F), C12(H12E,H12F), C13(H13E,H13F), C16(H16C,H16D), C17(H17C,
 H17D), C19(H19C,H19D), C13A(H13A,H13B), C13A(H13C,H13D), C16A(H16A,H16B),
 C17A(H17A,H17B), C19A(H19A,H19B), C11A(H11A,H11B), C12A(H12A,H12B), C11B(H11C,
 H11D), C12B(H12C,H12D)
5.c Aromatic/amide H refined with riding coordinates:
 N2(H2B), C1(H1), C2(H2C), C3(H3), C5(H5), C6(H6), C7(H7), C21(H21), C22(H22),
 C24(H24), C25(H25), N2A(H2AA), C1A(H1A), C2A(H2AB), C3A(H3A), C5A(H5A),
 C6A(H6A), C7A(H7A), C21A(H21A), C22A(H22A), C24A(H24A), C25A(H25A)
5.d Idealised tetrahedral OH refined as rotating group:
 O2(H2), O2A(H2A)
;
_shelx_res_checksum              8243
_shelx_hkl_checksum              20762
_olex2_submission_special_instructions 'No special instructions were received'