Direct enantioselective Mannich reactions of α-azido cyclic ketones: asymmetric construction of chiral azides possessing an α-quaternary stereocenter.
Ye, Xueqian; Pan, Yongkai; Yang, Xiaoyu; Chemical communications (Cambridge, England) 56 (2019) 98–101; doi:10.1039/c9cc08000g

data_7125431
_publ_section_title
;
 Direct enantioselective Mannich reactions of \a-azido cyclic ketones:
 asymmetric construction of chiral azides possessing an \a-quaternary
 stereocenter.
;
_journal_issue                   1
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              98
_journal_page_last               101
_journal_paper_doi               10.1039/c9cc08000g
_journal_volume                  56
_journal_year                    2019
_chemical_formula_moiety         'C22 H27 N3 O2'
_chemical_formula_sum            'C22 H27 N3 O2'
_chemical_formula_weight         365.46
_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             2019-10-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-10-19 deposited with the CCDC.	2019-11-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.4379(2)
_cell_length_b                   10.5541(3)
_cell_length_c                   22.3081(6)
_cell_measurement_reflns_used    9890
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      74.45
_cell_measurement_theta_min      4.19
_cell_volume                     1986.64(9)
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.0
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.987
_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  0.0214
_diffrn_reflns_av_unetI/netI     0.0187
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            16588
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         74.442
_diffrn_reflns_theta_min         5.605
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.629
_exptl_absorpt_correction_T_max  0.7538
_exptl_absorpt_correction_T_min  0.6968
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.222
_exptl_crystal_description       block
_exptl_crystal_F_000             784
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.310
_refine_diff_density_min         -0.287
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 1662 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.08(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     250
_refine_ls_number_reflns         4017
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0405
_refine_ls_R_factor_gt           0.0398
_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^)+(0.0699P)^2^+0.4270P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1107
_refine_ls_wR_factor_ref         0.1115
_reflns_Friedel_coverage         0.743
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.988
_reflns_number_gt                3931
_reflns_number_total             4017
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc08000g2.cif
_cod_data_source_block           cu_wdl_0m
_cod_depositor_comments
'Adding full bibliography for 7125431--7125432.cif.'
_cod_database_code               7125431
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.940
_shelx_estimated_absorpt_t_min   0.885
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All N(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 N002(H002), C00B(H00G), C00F(H00H), C00G(H00I), C00H(H00J), C00I(H00K),
 C00L(H00O), C00M(H00P), C00N(H00Q)
2.b Idealised Me refined as rotating group:
 N004(H00A,H00B,H00C), N00A(H00D,H00E,H00F), C00K(H00L,H00M,H00N), C00P(H00R,
 H00S,H00T), C00Q(H00U,H00V,H00W), C00R(H00X,H00Y,H)
;
_olex2_submission_special_instructions 'No special instructions were received'