Structural and mechanistic studies of the base-induced Sommelet–Hauser rearrangement of N-α-branched benzylic azetidine-2-carboxylic acid-derived ammonium salts
Tayama, Eiji; Watanabe, Kazutoshi; Sotome, Sho; Org. Biomol. Chem.  (2017) –; doi:10.1039/C7OB01391D

data_7155784
_publ_section_title
;
 Structural and mechanistic studies of the base-induced Sommelet--Hauser
 rearrangement of N-\a-branched benzylic azetidine-2-carboxylic
 acid-derived ammonium salts
;
_journal_name_full               'Org. Biomol. Chem.'
_journal_paper_doi               10.1039/C7OB01391D
_journal_year                    2017
_chemical_absolute_configuration rm
_chemical_compound_source        'synthesis as described'
_chemical_formula_sum            'C41 H46 B N O2'
_chemical_formula_weight         595.6
_chemical_name_systematic        2a-BPh4
_space_group_IT_number           19
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      19
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_conform_dict_location     ftp://ftp.iucr.org/pub/cif_core.dic
_audit_conform_dict_name         cif_core.dic
_audit_conform_dict_version      2.4.3
_audit_creation_date             2017-04-26T12:01:23-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_audit_update_record
;
2017-05-30 deposited with the CCDC.
2017-07-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.4025(10)
_cell_length_b                   15.8388(12)
_cell_length_c                   16.5989(13)
_cell_measurement_reflns_used    27280
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.6
_cell_measurement_theta_min      3.04
_cell_measurement_wavelength     0.71073
_cell_volume                     3523.6(5)
_computing_cell_refinement       'CrystalClear (Rigaku/MSC Inc., 2006)'
_computing_data_collection       'CrystalClear (Rigaku/MSC Inc., 2006)'
_computing_data_reduction
'CrystalClear (Rigaku/MSC Inc., 2006), SORTAV (Blessing, 1995)'
_computing_molecular_graphics    'Ortep-3 for Windows (Farrugia, 2012)'
_computing_publication_material  'WinGX publication routines (Farrugia, 2012)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2014)'
_computing_structure_solution    'SIR-2014 (Burla et al., 2014)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'quarter \C-circle diffractometer'
_diffrn_measurement_device_type  XTALAB-MINI
_diffrn_measurement_method       'phi or omega oscillation scans'
_diffrn_orient_matrix_UB_11      -0.063528
_diffrn_orient_matrix_UB_12      0.032506
_diffrn_orient_matrix_UB_13      -0.006019
_diffrn_orient_matrix_UB_21      -0.020581
_diffrn_orient_matrix_UB_22      -0.037984
_diffrn_orient_matrix_UB_23      -0.045162
_diffrn_orient_matrix_UB_31      -0.033283
_diffrn_orient_matrix_UB_32      -0.038558
_diffrn_orient_matrix_UB_33      0.039416
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.036
_diffrn_reflns_av_unetI/netI     0.0315
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            36211
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.484
_diffrn_reflns_theta_min         3.04
_diffrn_source                   'sealed x-ray tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.067
_exptl_absorpt_correction_T_max  0.986
_exptl_absorpt_correction_T_min  0.919
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'REQAB (Rigaku, 1998)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.123
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Prism
_exptl_crystal_F_000             1280
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.21
_refine_diff_density_max         0.121
_refine_diff_density_min         -0.122
_refine_diff_density_rms         0.023
_refine_ls_abs_structure_details
;
 Flack x determined using 1927 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.2(4)
_refine_ls_extinction_coef       0.0030(9)
_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   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     407
_refine_ls_number_reflns         8075
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.0805
_refine_ls_R_factor_gt           0.0442
_refine_ls_shift/su_max          0
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0478P)^2^+0.2267P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0939
_refine_ls_wR_factor_ref         0.1085
_reflns_Friedel_coverage         0.802
_reflns_Friedel_fraction_full    1
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                5347
_reflns_number_total             8075
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ob01391d2.cif
_cod_data_source_block           shelx_CCDC1
_cod_database_code               7155784
_shelx_estimated_absorpt_t_min   0.977
_shelx_estimated_absorpt_t_max   0.986