Strain-release C-C bond cleavage enables the [2,3]-sigmatropic rearrangement of tertiary allylamines.
Dai, Rui-Han; Han, Lu; Wang, Qi; Tian, Shi-Kai; Chemical communications (Cambridge, England) 57 (2021) 8449–8451; doi:10.1039/d1cc03141d

data_7128691
_publ_section_title
;
 Strain-release C-C bond cleavage enables the [2,3]-sigmatropic
 rearrangement of tertiary allylamines.
;
_journal_issue                   68
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              8449
_journal_page_last               8451
_journal_paper_doi               10.1039/d1cc03141d
_journal_volume                  57
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H22 F2 N2 O3 S'
_chemical_formula_sum            'C22 H22 F2 N2 O3 S'
_chemical_formula_weight         432.47
_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
_audit_creation_date             2021-03-12
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-03-12 deposited with the CCDC.	2021-07-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.36756(12)
_cell_length_b                   11.59613(14)
_cell_length_c                   17.36693(19)
_cell_measurement_reflns_used    6078
_cell_measurement_temperature    291(2)
_cell_measurement_theta_max      70.0620
_cell_measurement_theta_min      3.7860
_cell_volume                     2087.91(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      291(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2169
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -63.00 -33.00   1.00    2.00    --  -40.80  38.00  30.00   30
  2  \w    -29.00  10.00   1.00    2.00    --  -40.80  38.00  30.00   39
  3  \w    -73.00  35.00   1.00    2.00    --  -40.80  77.00 -90.00  108
  4  \w    110.00 153.00   1.00    4.00    --   99.68 125.00   0.00   43
  5  \w     99.00 173.00   1.00    4.00    --   99.68 125.00 -60.00   74
  6  \w    107.00 167.00   1.00    4.00    --   99.68 125.00 150.00   60
  7  \w    100.00 138.00   1.00    4.00    --   99.68 125.00-180.00   38
  8  \w     80.00 173.00   1.00    4.00    --   99.68  45.00 120.00   93
  9  \w     19.00 100.00   1.00    4.00    --   99.68 -94.00  90.00   81
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0407299000
_diffrn_orient_matrix_UB_12      0.1120297000
_diffrn_orient_matrix_UB_13      -0.0410365000
_diffrn_orient_matrix_UB_21      0.1428356000
_diffrn_orient_matrix_UB_22      0.0300376000
_diffrn_orient_matrix_UB_23      -0.0139607000
_diffrn_orient_matrix_UB_31      -0.0042036000
_diffrn_orient_matrix_UB_32      -0.0647976000
_diffrn_orient_matrix_UB_33      -0.0773927000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0190
_diffrn_reflns_av_unetI/netI     0.0224
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            7580
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.823
_diffrn_reflns_theta_min         4.585
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.766
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66550
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.376
_exptl_crystal_description       block
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.252
_refine_diff_density_min         -0.209
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 1562 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.027(7)
_refine_ls_extinction_coef       0.0031(5)
_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   1.089
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     273
_refine_ls_number_reflns         3856
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0367
_refine_ls_R_factor_gt           0.0361
_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^)+(0.0609P)^2^+0.2791P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0996
_refine_ls_wR_factor_ref         0.1003
_reflns_Friedel_coverage         0.728
_reflns_Friedel_fraction_full    0.986
_reflns_Friedel_fraction_max     0.958
_reflns_number_gt                3768
_reflns_number_total             3856
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc03141d2.cif
_cod_data_source_block           drh12-99-12
_cod_depositor_comments
'Adding full bibliography for 7128691--7128692.cif.'
_cod_database_code               7128691
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         c20h20o2n2s2f3
_shelx_estimated_absorpt_t_max   0.765
_shelx_estimated_absorpt_t_min   0.697
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     64.99
_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. Rigid bond restraints
 N1, C7
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
3.a Ternary CH refined with riding coordinates:
 C8(H8), C12(H12), C14(H14)
3.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C13(H13A,H13B), C9(H9A,H9B)
3.c Aromatic/amide H refined with riding coordinates:
 C18(H18), C22(H22), C20(H20), C5(H5), C2(H2), C10(H10), C4(H4), C3(H3)
3.d X=CH2 refined with riding coordinates:
 C11(H11A,H11B)
3.e Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.470
_oxdiff_exptl_absorpt_empirical_full_min 0.661