Pd-Catalyzed Umpolung Asymmetric Allylic Alkylation of Hydrazones to Vicinal Tertiary and Quaternary Chiral Carbon Centers
Huang, Shuai; Zhang, Gao-Peng; Jiang, Yang-Jie; Yu, Fei-Le; Ding, Chang-Hua; Hou, Xuelong; Chemical Communications  (2022) –; doi:10.1039/D1CC07074F

data_7129706
_publ_section_title
;
 Pd-Catalyzed Umpolung Asymmetric Allylic Alkylation of Hydrazones to
 Vicinal Tertiary and Quaternary Chiral Carbon Centers
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC07074F
_journal_year                    2022
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C22 H24 Br N O'
_chemical_formula_sum            'C22 H24 Br N O'
_chemical_formula_weight         398.33
_space_group_crystal_system      hexagonal
_space_group_IT_number           170
_space_group_name_Hall           'P 65'
_space_group_name_H-M_alt        'P 65'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2016-11-22
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5261)
;
_audit_update_record
;
2020-03-24 deposited with the CCDC.	2022-02-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   12.716(2)
_cell_length_b                   12.716(2)
_cell_length_c                   22.693(4)
_cell_measurement_reflns_used    4606
_cell_measurement_temperature    130
_cell_measurement_theta_max      23.936
_cell_measurement_theta_min      2.58
_cell_volume                     3177.8(9)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_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      130
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0881
_diffrn_reflns_av_unetI/netI     0.0988
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            28556
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.822
_diffrn_reflns_theta_min         1.849
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.949
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.4240
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1109 before and 0.0793 after correction.
The Ratio of minimum to maximum transmission is 0.5685.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.249
_exptl_crystal_description       block
_exptl_crystal_F_000             1236
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.403
_refine_diff_density_min         -0.329
_refine_diff_density_rms         0.066
_refine_ls_abs_structure_details
;
 Flack x determined using 1342 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.034(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     226
_refine_ls_number_reflns         5400
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0872
_refine_ls_R_factor_gt           0.0531
_refine_ls_shift/su_max          0.049
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0121P)^2^+2.1858P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1132
_refine_ls_wR_factor_ref         0.1247
_reflns_Friedel_coverage         0.916
_reflns_Friedel_fraction_full    0.979
_reflns_Friedel_fraction_max     0.956
_reflns_number_gt                3893
_reflns_number_total             5400
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc07074f2.cif
_cod_data_source_block           mo_dm16776_0m
_cod_original_cell_volume        3177.7(12)
_cod_database_code               7129706
_shelx_estimated_absorpt_t_max   0.909
_shelx_estimated_absorpt_t_min   0.759
_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.a Ternary CH refined with riding coordinates:
 C1(H1A)
2.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B)
2.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C2(H2), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C18(H18), C19(H19),
 C21(H21), C22(H22)
2.d X=CH2 refined with riding coordinates:
 C3(H3A,H3B)
;
_shelx_res_checksum              51902
_shelx_fab_checksum              79189
_shelx_shelxl_version_number     2016/6
_olex2_submission_special_instructions 'No special instructions were received'