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_7125432
_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         'C19 H28 N4 O4'
_chemical_formula_sum            'C19 H28 N4 O4'
_chemical_formula_weight         376.45
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-11-13
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-11-15 deposited with the CCDC.	2019-11-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.952(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.1314(4)
_cell_length_b                   10.4464(4)
_cell_length_c                   15.7145(6)
_cell_measurement_reflns_used    9830
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      78.46
_cell_measurement_theta_min      3.66
_cell_volume                     1980.75(13)
_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      150.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.992
_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  0.0787
_diffrn_reflns_av_unetI/netI     0.0563
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            42305
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         79.319
_diffrn_reflns_theta_min         2.827
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.734
_exptl_absorpt_correction_T_max  0.7542
_exptl_absorpt_correction_T_min  0.4948
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1648 before and 0.0974 after correction.
The Ratio of minimum to maximum transmission is 0.6561.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.262
_exptl_crystal_description       block
_exptl_crystal_F_000             808
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.289
_refine_diff_density_min         -0.320
_refine_diff_density_rms         0.063
_refine_ls_abs_structure_details
;
 Flack x determined using 3006 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.15(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     497
_refine_ls_number_reflns         8391
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0625
_refine_ls_R_factor_gt           0.0538
_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^)+(0.0420P)^2^+1.8135P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1273
_refine_ls_wR_factor_ref         0.1339
_reflns_Friedel_coverage         0.860
_reflns_Friedel_fraction_full    0.988
_reflns_Friedel_fraction_max     0.954
_reflns_number_gt                7424
_reflns_number_total             8391
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc08000g2.cif
_cod_data_source_block           cu_yxq51271_0m
_cod_depositor_comments
'Adding full bibliography for 7125431--7125432.cif.'
_cod_database_code               7125432
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.867
_shelx_estimated_absorpt_t_min   0.758
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C00L(H00L), C00Q(H00Q), C00Z(H00Z), C012(H012)
2.b Secondary CH2 refined with riding coordinates:
 C00T(H00A,H00B), C00U(H00D,H00E), C010(H01A,H01B), C014(H01C,H01D), C016(H01S,
 H01T), C018(H01E,H01F), C01B(H01Z,HA), C01D(H01,HB)
2.c Aromatic/amide H refined with riding coordinates:
 N009(H009), N00A(H00C), C00H(H00H), C00K(H00K), C00N(H00N), C00O(H00O),
 C00S(H00S), C00W(H00W), C00X(H00X), C011(H011)
2.d Idealised Me refined as rotating group:
 C017(H01U,H01V,H01W), C019(H01X,H01Y,H), C01C(H01G,H01H,H01I), C01E(H01J,H01K,
 H01L), C01F(H01M,H01N,H01O), C01G(H0AA,HC,HD), C01H(H1AA,HE,HF), C01I(H01P,
 H01Q,H01R)
2.e Idealised tetrahedral OH refined as rotating group:
 O001(H001), O002(H002)
;
_shelx_res_checksum              92802
_olex2_submission_special_instructions 'No special instructions were received'