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_7129707
_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 ad
_chemical_formula_sum            'C17 H21 N'
_chemical_formula_weight         239.35
_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
_audit_creation_method           SHELXL-2013
_audit_update_record
;
2020-03-24 deposited with the CCDC.	2022-02-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.5730(10)
_cell_angle_gamma                90
_cell_formula_units_Z            6
_cell_length_a                   6.06320(10)
_cell_length_b                   31.1441(6)
_cell_length_c                   11.8320(2)
_cell_measurement_reflns_used    9826
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      140.179
_cell_measurement_theta_min      5.675
_cell_volume                     2171.87(7)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.963
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0384
_diffrn_reflns_av_unetI/netI     0.0285
_diffrn_reflns_Laue_measured_fraction_full 0.963
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            34262
_diffrn_reflns_point_group_measured_fraction_full 0.961
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         66.985
_diffrn_reflns_theta_min         2.838
_exptl_absorpt_coefficient_mu    0.474
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.5301
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.098
_exptl_crystal_description       prismatic
_exptl_crystal_F_000             780
_exptl_crystal_size_max          0.190
_exptl_crystal_size_mid          0.160
_exptl_crystal_size_min          0.130
_refine_diff_density_max         0.105
_refine_diff_density_min         -0.098
_refine_diff_density_rms         0.020
_refine_ls_abs_structure_details
; 
 Flack x determined using 3321 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons and Flack (2004), Acta Cryst. A60, s61). 
;
_refine_ls_abs_structure_Flack   -0.13(17)
_refine_ls_extinction_coef       0.0110(17)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     518
_refine_ls_number_reflns         7552
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0371
_refine_ls_R_factor_gt           0.0348
_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^)+(0.0488P)^2^+0.1304P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0892
_refine_ls_wR_factor_ref         0.0915
_reflns_Friedel_coverage         0.956
_reflns_Friedel_fraction_full    0.959
_reflns_Friedel_fraction_max     0.974
_reflns_number_gt                7176
_reflns_number_total             7552
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc07074f2.cif
_cod_data_source_block           cu_d8v19809_0m
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               7129707
_shelx_estimated_absorpt_t_min   0.915
_shelx_estimated_absorpt_t_max   0.941
_shelxl_version_number           2013-4
_shelx_res_checksum              18103