Diastereoselective Synthesis of 1,3-Diyne-Tethered Trifluoromethyl-Cyclopropanes through Sulfur Ylides-Mediated Cyclopropanation/ DBU-Mediated Epimerization Sequence.
Chen, Guo-Shu; Yan, Xiaoxue; Chen, Shujie; Mao, Xiang-Yu; Li, Zhao-Dong; Liu, Yunlin; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c00162

data_4038284
_publ_section_title
;
 Diastereoselective Synthesis of 1,3-Diyne-Tethered
 Trifluoromethyl-Cyclopropanes through Sulfur Ylides-Mediated
 Cyclopropanation/ DBU-Mediated Epimerization Sequence.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c00162
_journal_year                    2020
_chemical_formula_moiety         'C22 H13 Br F3 N O2'
_chemical_formula_sum            'C22 H13 Br F3 N O2'
_chemical_formula_weight         460.24
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-11-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                89.593(7)
_cell_angle_beta                 79.654(13)
_cell_angle_gamma                86.612(12)
_cell_formula_units_Z            4
_cell_length_a                   7.3293(13)
_cell_length_b                   14.6561(14)
_cell_length_c                   18.0368(11)
_cell_measurement_reflns_used    3053
_cell_measurement_temperature    99.98(11)
_cell_measurement_theta_max      25.5100
_cell_measurement_theta_min      2.8210
_cell_volume                     1902.6(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (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_environment      N~2~
_diffrn_ambient_temperature      99.98(11)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.825
_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    -22.00  53.00   1.00    8.00    --  -11.59  77.00 -60.00   75
  2  \w     -9.00  47.00   1.00    8.00    --   11.74  77.00  60.00   56
  3  \w    -84.00  12.00   1.00    9.00    --  -11.66 -57.00-180.00   96
  4  \w     35.00  77.00   1.00    9.00    --   11.66 178.00-180.00   42
  5  \w    -61.00 -34.00   1.00    9.00    --   11.66 -57.00 120.00   27
  6  \w     -2.00  23.00   1.00    9.00    --   11.66 -57.00 120.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0219354000
_diffrn_orient_matrix_UB_12      -0.0463106000
_diffrn_orient_matrix_UB_13      0.0057345000
_diffrn_orient_matrix_UB_21      0.0611124000
_diffrn_orient_matrix_UB_22      -0.0123452000
_diffrn_orient_matrix_UB_23      -0.0340169000
_diffrn_orient_matrix_UB_31      0.0741441000
_diffrn_orient_matrix_UB_32      -0.0073032000
_diffrn_orient_matrix_UB_33      0.0201985000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0775
_diffrn_reflns_av_unetI/netI     0.1431
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.825
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            16151
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.825
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.524
_diffrn_reflns_theta_min         2.296
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.207
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.43288
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.607
_exptl_crystal_description       block
_exptl_crystal_F_000             920
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         4.506
_refine_diff_density_min         -1.902
_refine_diff_density_rms         0.294
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.338
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     518
_refine_ls_number_reflns         8756
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.338
_refine_ls_R_factor_all          0.2049
_refine_ls_R_factor_gt           0.1485
_refine_ls_shift/su_max          0.038
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3920
_refine_ls_wR_factor_ref         0.4268
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5165
_reflns_number_total             8756
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00162_si_002.cif
_cod_data_source_block           cgj-3-2
_cod_database_code               4038284
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.793
_shelx_estimated_absorpt_t_min   0.747
_reflns_odcompleteness_completeness 98.32
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C1(H1), C1B(H1B)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C2B(H2BA,H2BB)
2.c Aromatic/amide H refined with riding coordinates:
 C17B(H17B), C14(H14), C14B(H14B), C9B(H9B), C20(H20), C18(H18), C10B(H10B),
 C9(H9), C19(H19), C7B(H7B), C21B(H21B), C6B(H6B), C10(H10), C7(H7), C20B(H20B),
  C6(H6), C19B(H19B), C18B(H18B), C17(H17), C21(H21)
;
_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 1.602
_oxdiff_exptl_absorpt_empirical_full_min 0.680