Electrochemical synthesis of 7-membered carbocycles through cascade 5-exo-trig/7-endo-trig radical cyclization
Long, Hao; Song, Jinshuai; Xu, Hai-Chao; Organic Chemistry Frontiers 5 (2018) 3129–; doi:10.1039/C8QO00803E

data_1554414
_publ_section_title
;
 Electrochemical synthesis of 7-membered carbocycles through cascade
 5-exo-trig/7-endo-trig radical cyclization
;
_journal_issue                   21
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              3129
_journal_paper_doi               10.1039/C8QO00803E
_journal_volume                  5
_journal_year                    2018
_chemical_formula_moiety         'C19 H24 F3 N O2'
_chemical_formula_sum            'C19 H24 F3 N O2'
_chemical_formula_weight         355.39
_chemical_name_systematic        7-endo
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-01-09
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-02-09 deposited with the CCDC.
2018-09-26 downloaded from the CCDC.
;
_cell_angle_alpha                76.939(7)
_cell_angle_beta                 79.228(7)
_cell_angle_gamma                63.194(9)
_cell_formula_units_Z            4
_cell_length_a                   12.1127(10)
_cell_length_b                   13.1333(12)
_cell_length_c                   13.1505(11)
_cell_measurement_reflns_used    3719
_cell_measurement_temperature    173
_cell_measurement_theta_max      62.1290
_cell_measurement_theta_min      3.4440
_cell_volume                     1810.2(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 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      173
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1903
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.981
_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      9.00  95.00   1.00    1.00    --   32.31  77.00 -60.00   86
  2  \w     32.00  87.00   1.00    1.00    --   32.31  57.00-120.00   55
  3  \w     70.00 164.00   1.00    2.40    --   94.50  50.00-180.00   94
  4  \w     92.00 120.00   1.00    2.40    --   94.50 -50.00-180.00   28
  5  \w     71.00 122.00   1.00    2.40    --   94.50 -92.00-150.00   51
  6  \w     74.00 101.00   1.00    2.40    --   94.50 -92.00 -60.00   27
  7  \w     35.00 121.00   1.00    2.40    --   94.50 -93.00  16.72   86
  8  \w     75.00 135.00   1.00    2.40    --   94.50 -92.00  90.00   60
  9  \w     74.00  99.00   1.00    2.40    --   94.50 -92.00 150.00   25
 10  \w     25.00 120.00   1.00    2.40    --   94.50 -64.00  30.00   95
 11  \w     73.00 167.00   1.00    2.40    --   94.50  38.00 120.00   94
 12  \w    121.00 147.00   1.00    2.40    --   94.50  50.00 150.00   26
 13  \w    119.00 164.00   1.00    2.40    --   94.50  64.00  60.00   45
 14  \w    115.00 168.00   1.00    2.40    --   94.50  38.00  30.00   53
 15  \w    109.00 135.00   1.00    2.40    --   94.50 112.00   0.00   26
 16  \w     84.00 115.00   1.00    2.40    --   94.50  64.00  60.00   31
 17  \w     80.00 113.00   1.00    2.40    --   94.50  50.00 150.00   33
 18  \w     65.00 110.00   1.00    2.40    --   94.50  38.00  30.00   45
 19  \w     25.00  51.00   1.00    2.40    --   94.50 -92.00-150.00   26
 20  \w     24.00  68.00   1.00    2.40    --   94.50 -50.00-180.00   44
 21  \w     24.00 113.00   1.00    2.40    --   94.50 -92.00 -90.00   89
 22  \w     22.00  56.00   1.00    2.40    --   94.50 -92.00-180.00   34
 23  \w    -25.00  77.00   1.00    1.00    --   32.31 -99.00-180.00  102
 24  \w     22.00  67.00   1.00    2.40    --   94.50-105.00 -10.00   45
 25  \w    -86.00  31.00   1.00    1.00    --  -32.31 -19.00 -30.00  117
 26  \w   -106.00 -77.00   1.00    1.00    --  -32.31-178.00 -30.00   29
 27  \w   -111.00 -78.00   1.00    1.00    --  -32.31 178.00-120.00   33
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1048474000
_diffrn_orient_matrix_UB_12      -0.0145959000
_diffrn_orient_matrix_UB_13      -0.0900712000
_diffrn_orient_matrix_UB_21      -0.0946698000
_diffrn_orient_matrix_UB_22      0.0931089000
_diffrn_orient_matrix_UB_23      -0.0740646000
_diffrn_orient_matrix_UB_31      0.0233827000
_diffrn_orient_matrix_UB_32      0.0940938000
_diffrn_orient_matrix_UB_33      0.0316784000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0454
_diffrn_reflns_av_unetI/netI     0.0609
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            10843
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        62.282
_diffrn_reflns_theta_max         62.282
_diffrn_reflns_theta_min         3.467
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.884
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60249
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.304
_exptl_crystal_description       block
_exptl_crystal_F_000             752
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.5
_refine_diff_density_max         1.106
_refine_diff_density_min         -0.451
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     462
_refine_ls_number_reflns         5620
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0851
_refine_ls_R_factor_gt           0.0762
_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^)+(0.1330P)^2^+0.9880P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2009
_refine_ls_wR_factor_ref         0.2149
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4708
_reflns_number_total             5620
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8qo00803e5.cif
_cod_data_source_block           exp_18359
_cod_database_code               1554414
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.666
_shelx_estimated_absorpt_t_min   0.666
_reflns_odcompleteness_completeness 99.51
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     61.08
_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:
 C00F(H00F), C00G(H00G), C00H(H00H), C00J(H00J), C00K(H00K), C00T(H00T)
2.b Secondary CH2 refined with riding coordinates:
 C00N(H00A,H00B), C00R(H00C,H00E), C00V(H00I,H00N), C00X(H00Q,H00R), C012(H01C,
 H01D), C013(H01E,H01F), C014(H01N,H01O), C015(H01G,H01H), C016(H01P,H01Q),
 C018(H01R,H01S), C01A(H01I,H01J), C01B(H01T,H01U), C01C(H01V,H01W)
2.c Aromatic/amide H refined with riding coordinates:
 C00D(H00D), C00L(H00L), C00M(H00M), C00O(H00O), C00P(H00P), C00W(H00W),
 C00Y(H00Y), C010(H010)
2.d Idealised Me refined as rotating group:
 C01D(H01K,H01L,H01M), C01E(H01X,H01Y,H)
;
_shelx_res_checksum              22984
_shelx_hkl_checksum              12015
_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 2.057
_oxdiff_exptl_absorpt_empirical_full_min 0.540