Ring Expansion of Bicyclic Methyleneaziridines via Concerted, Near-Barrierless [2,3]-Stevens Rearrangements of Aziridinium Ylides.
Schmid, Steven C.; Guzei, Ilia A.; Fernández, Israel; Schomaker, Jennifer M.; ACS catalysis 8 (2018) 7907–7914; doi:10.1021/acscatal.8b02206

data_4515743
_publ_section_title
;
 Ring Expansion of Bicyclic Methyleneaziridines via Concerted,
 Near-Barrierless [2,3]-Stevens Rearrangements of Aziridinium Ylides.
;
_journal_issue                   9
_journal_name_full               'ACS catalysis'
_journal_page_first              7907
_journal_page_last               7914
_journal_paper_doi               10.1021/acscatal.8b02206
_journal_volume                  8
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H24 Cl N O4'
_chemical_formula_sum            'C20 H24 Cl N O4'
_chemical_formula_weight         377.85
_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             2017-08-17
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2017.07.20 svn.r3457 for OlexSys, GUI svn.r5370)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.174(11)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.421(3)
_cell_length_b                   16.048(6)
_cell_length_c                   8.176(3)
_cell_measurement_reflns_used    4481
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.483
_cell_measurement_theta_min      2.538
_cell_volume                     955.2(6)
_computing_cell_refinement       'APEX3 Ver. 2017.3-0 (Bruker-AXS, 2017)'
_computing_data_collection       'APEX3 Ver. 2017.3-0 (Bruker-AXS, 2017)'
_computing_data_reduction        'APEX3 Ver. 2017.3-0 (Bruker-AXS, 2017)'
_computing_molecular_graphics    'OLEX2 (Dolomanov et al., 2009)'
_computing_publication_material  'OLEX2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2015b)'
_computing_structure_solution    'XT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'charge-coupled device (CCD) area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker APEX II'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX II Quazar'
_diffrn_measurement_method       '0.5\% \w and 0.5\% \f scans'
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_detector       'Bruker APEX II'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0422
_diffrn_reflns_av_unetI/netI     0.0496
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            16434
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         28.316
_diffrn_reflns_theta_min         2.538
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    0.225
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.7125
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Krause et al., 2015) was used for absorption correction.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.314
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             400
_exptl_crystal_size_max          0.064
_exptl_crystal_size_mid          0.048
_exptl_crystal_size_min          0.027
_refine_diff_density_max         0.258
_refine_diff_density_min         -0.196
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 1621 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.04(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     237
_refine_ls_number_reflns         4616
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0472
_refine_ls_R_factor_gt           0.0362
_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^)+(0.0427P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0774
_refine_ls_wR_factor_ref         0.0809
_reflns_Friedel_coverage         0.884
_reflns_Friedel_fraction_full    0.972
_reflns_Friedel_fraction_max     0.944
_reflns_number_gt                3955
_reflns_number_total             4616
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b02206_si_002.cif
_cod_data_source_block           schomaker81
_cod_original_cell_volume        955.3(6)
_cod_database_code               4515743
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.994
_shelx_estimated_absorpt_t_min   0.986
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C2(H2)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B), C18(H18A,
 H18B), C19(H19A,H19B)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C17(H17)
2.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C16(H16A,H16B,H16C)
;
_shelx_res_checksum              13125
_shelx_hkl_checksum              42276
_olex2_submission_special_instructions 'No special instructions were received'