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_7155783
_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_compound_source        'synthesis as described'
_chemical_formula_sum            'C42 H46 B N O2'
_chemical_formula_weight         607.60
_chemical_name_systematic        2e-BPh4
_space_group_IT_number           1
_symmetry_cell_setting           triclinic
_symmetry_Int_Tables_number      1
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     'direct - structure invariant direct methods'
_atom_sites_solution_secondary   'direct - structure invariant direct methods'
_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             2017-04-19T13:24:39-00:00
_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                79.125(6)
_cell_angle_beta                 89.681(6)
_cell_angle_gamma                62.353(4)
_cell_formula_units_Z            2
_cell_length_a                   10.1389(13)
_cell_length_b                   10.2830(13)
_cell_length_c                   19.617(3)
_cell_measurement_reflns_used    15228
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.63
_cell_measurement_theta_min      2.98
_cell_measurement_wavelength     0.71073
_cell_volume                     1771.3(4)
_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-2011 (Burla et al., 2012)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.994
_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      0.005608
_diffrn_orient_matrix_UB_12      -0.043688
_diffrn_orient_matrix_UB_13      0.050628
_diffrn_orient_matrix_UB_21      0.107316
_diffrn_orient_matrix_UB_22      -0.073813
_diffrn_orient_matrix_UB_23      -0.001111
_diffrn_orient_matrix_UB_31      0.030989
_diffrn_orient_matrix_UB_32      0.072468
_diffrn_orient_matrix_UB_33      0.012418
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0233
_diffrn_reflns_av_unetI/netI     0.0549
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            18195
_diffrn_reflns_point_group_measured_fraction_full 0.976
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.482
_diffrn_reflns_theta_min         2.982
_diffrn_source                   'sealed x-ray tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.068
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.139
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Prism
_exptl_crystal_F_000             652
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.187
_refine_diff_density_min         -0.152
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 4314 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.1(8)
_refine_ls_extinction_coef       0.0058(14)
_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   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     830
_refine_ls_number_reflns         15384
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0835
_refine_ls_R_factor_gt           0.0552
_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^)+(0.0432P)^2^+0.2378P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1118
_refine_ls_wR_factor_ref         0.1265
_reflns_Friedel_coverage         0.903
_reflns_Friedel_fraction_full    0.955
_reflns_Friedel_fraction_max     0.898
_reflns_number_gt                11094
_reflns_number_total             15384
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ob01391d2.cif
_cod_data_source_block           shelx
_cod_depositor_comments
;

2017-11-16
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum        'C84 H92 B2 N2 O4'
_cod_original_formula_units_Z    1
_cod_original_formula_weight     1215.21
_cod_database_code               7155783
_shelx_estimated_absorpt_t_min   0.98
_shelx_estimated_absorpt_t_max   0.989