Regio- and Enantioselective Bromocyclization of Difluoroalkenes as a Strategy to Access Tetrasubstituted Difluoromethylene-Containing Stereocenters.
Miller, Edward; Kim, Suhong; Gibson, Katarina; Derrick, Jeffrey S.; Toste, F. Dean; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c02331

data_4134873
_publ_section_title
;
 Regio- and Enantioselective Bromocyclization of Difluoroalkenes as a
 Strategy to Access Tetrasubstituted Difluoromethylene-Containing
 Stereocenters.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c02331
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C17 H19 Br F2 N O, Cl'
_chemical_formula_sum            'C17 H19 Br Cl F2 N O'
_chemical_formula_weight         406.69
_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             2020-02-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 104.8306(17)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.3777(2)
_cell_length_b                   6.86536(10)
_cell_length_c                   11.42344(18)
_cell_measurement_reflns_used    11764
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      78.6330
_cell_measurement_theta_min      3.9520
_cell_volume                     862.58(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_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      100(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_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    -20.00  45.00   0.50    0.50    --    0.00  77.00-150.00  130
  2  \w    -20.00  45.00   0.50    0.50    --    0.00  77.00 -30.00  130
  3  \w    -20.00  45.00   0.50    0.50    --    0.00  77.00   0.00  130
  4  \w    -20.00  45.00   0.50    0.50    --    0.00  77.00  60.00  130
  5  \w    -77.00   8.00   0.50    0.50    --    0.00   0.00 150.00  170
  6  \w     31.00  68.00   0.50    0.50    --  106.00 -94.00  30.00   74
  7  \w     30.00 107.00   0.50    0.50    --  106.00 -99.00 169.00  154
  8  \w     30.00 109.00   0.50    0.50    --  106.00-111.00 150.00  158
  9  \w     30.00 109.00   0.50    0.50    --  106.00-111.00 -60.00  158
 10  \w     30.00 106.00   0.50    0.50    --  106.00 -94.00 -60.00  152
 11  \w     38.00  67.00   0.50    0.50    --  106.00-111.00-120.00   58
 12  \w     73.00 107.00   0.50    0.50    --  106.00-111.00-120.00   68
 13  \w     30.00 103.00   0.50    0.50    --  106.00 -94.00-150.00  146
 14  \w     74.00 103.00   0.50    0.50    --  106.00 -94.00  30.00   58
 15  \w     30.00 106.00   0.50    0.50    --  106.00 -94.00 150.00  152
 16  \w     36.00  68.00   0.50    0.50    --  106.00 -61.00  30.00   64
 17  \w     36.00  68.00   0.50    0.50    --  106.00 -61.00  90.00   64
 18  \w     34.00 102.00   0.50    0.50    --  106.00 -77.00  30.00  136
 19  \w     34.00  73.00   0.50    0.50    --  106.00 -77.00 -30.00   78
 20  \w     34.00 102.00   0.50    0.50    --  106.00 -77.00 -60.00  136
 21  \w     36.00  68.00   0.50    0.50    --  106.00 -61.00 150.00   64
 22  \w     84.00 175.00   0.50    0.50    --  106.00  99.00 -84.00  182
 23  \w     89.00 158.00   0.50    0.50    --  106.00  77.00  60.00  138
 24  \w     97.00 175.00   0.50    0.50    --  106.00  45.00 120.00  156
 25  \w     89.00 175.00   0.50    0.50    --  106.00  69.00-127.34  172
 26  \w   -107.00 -24.00   0.50    0.50    -- -100.00  99.00 -84.00  166
 27  \w   -109.00 -24.00   0.50    0.50    -- -100.00 111.00-180.00  170
 28  \w    -74.00 -30.00   0.50    0.50    -- -100.00  61.00-120.00   88
 29  \w    -54.00 -25.00   0.50    0.50    -- -100.00  45.00-120.00   58
 30  \w    -54.00 -25.00   0.50    0.50    -- -100.00  45.00-180.00   58
 31  \w    -54.00 -25.00   0.50    0.50    -- -100.00  45.00-150.00   58
 32  \w    -74.00 -30.00   0.50    0.50    -- -100.00  61.00 -90.00   88
 33  \w    -54.00 -25.00   0.50    0.50    -- -100.00  45.00 -90.00   58
 34  \w    -54.00 -25.00   0.50    0.50    -- -100.00  45.00 -60.00   58
 35  \w    -54.00 -25.00   0.50    0.50    -- -100.00  45.00  90.00   58
 36  \w   -109.00 -24.00   0.50    0.50    -- -100.00 111.00 120.00  170
 37  \w   -177.00 -94.00   0.50    0.50    -- -100.00 -30.00  30.00  166
 38  \w   -171.00 -87.00   0.50    0.50    -- -100.00 -58.00  19.32  168
 39  \w   -171.00 -82.00   0.50    0.50    -- -100.00 -72.00-133.07  178
 40  \w   -169.00 -85.00   0.50    0.50    -- -100.00 -64.00-138.92  168
 41  \w   -170.00 -86.00   0.50    0.50    -- -100.00 -61.00-154.05  168
 42  \w   -170.00 -86.00   0.50    0.50    -- -100.00 -61.00-164.22  168
 43  \w   -177.00 -94.00   0.50    0.50    -- -100.00 -30.00 -60.00  166
 44  \w   -176.00 -94.00   0.50    0.50    -- -100.00 -37.00  75.69  164
 45  \w   -176.00 -90.00   0.50    0.50    -- -100.00 -99.00 169.00  172
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom DW system, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0001649000
_diffrn_orient_matrix_UB_12      0.1083159000
_diffrn_orient_matrix_UB_13      0.1180717000
_diffrn_orient_matrix_UB_21      -0.1396322000
_diffrn_orient_matrix_UB_22      -0.0161136000
_diffrn_orient_matrix_UB_23      -0.0304504000
_diffrn_orient_matrix_UB_31      0.0114352000
_diffrn_orient_matrix_UB_32      -0.1957717000
_diffrn_orient_matrix_UB_33      0.0678327000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0627
_diffrn_reflns_av_unetI/netI     0.0338
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            17716
_diffrn_reflns_point_group_measured_fraction_full 0.913
_diffrn_reflns_point_group_measured_fraction_max 0.895
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.967
_diffrn_reflns_theta_min         4.003
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.882
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67196
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.71a (Rigaku Oxford Diffraction, 2020)
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    1.566
_exptl_crystal_description       plate
_exptl_crystal_F_000             412
_exptl_crystal_size_max          0.52
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.117
_refine_diff_density_min         -0.632
_refine_diff_density_rms         0.112
_refine_ls_abs_structure_details
;
 Flack x determined using 1205 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.168
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     210
_refine_ls_number_reflns         3333
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.167
_refine_ls_R_factor_all          0.0545
_refine_ls_R_factor_gt           0.0531
_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^)+(0.0997P)^2^+0.8940P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1528
_refine_ls_wR_factor_ref         0.1551
_reflns_Friedel_coverage         0.662
_reflns_Friedel_fraction_full    0.808
_reflns_Friedel_fraction_max     0.780
_reflns_number_gt                3210
_reflns_number_total             3333
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c02331_si_003.cif
_cod_data_source_block           CF2Br_aminoalcohol
_cod_database_code               4134873
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C H O N Cl F Br'
_diffrn_oxdiff_digest_frames
;
013f0c68404fda3ea0e304ed754f7924b40560642e8
;
_diffrn_oxdiff_digest_hkl
;
01610a61d6e0942896cec7844a84e0abfa8b0b
;
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Others
 Fixed Uiso: H1(0.045) H1A(0.029) H1B(0.029) H2(0.035) H17(0.039) H5(0.041)
 H13(0.038) H14(0.045) H11A(0.031) H11B(0.031) H3(0.038) H6(0.037) H15(0.045)
 H10A(0.033) H10B(0.033) H16(0.044) H7A(0.061) H7B(0.061) H7C(0.061)
 Fixed X: H1(0.293364) H1A(0.4508) H1B(0.461782) H2(0.165965) H17(0.604572)
 H5(0.176574) H13(0.626084) H14(0.679002) H11A(0.590392) H11B(0.647386)
 H3(0.113294) H6(0.23921) H15(0.682523) H10A(0.351152) H10B(0.377153)
 H16(0.648285) H7A(0.014107) H7B(0.114107) H7C(0.144785)
 Fixed Y: H1(0.688089) H1A(0.380789) H1B(0.537815) H2(0.713474) H17(0.662116)
 H5(0.133625) H13(0.086149) H14(0.137963) H11A(0.196339) H11B(0.398985)
 H3(0.707749) H6(0.141382) H15(0.448284) H10A(0.189839) H10B(0.340205)
 H16(0.712618) H7A(0.386713) H7B(0.541637) H7C(0.318927)
 Fixed Z: H1(0.253346) H1A(0.42242) H1B(0.342852) H2(0.379797) H17(0.227479)
 H5(0.588156) H13(0.185005) H14(0.003656) H11A(0.362791) H11B(0.408946)
 H3(0.561667) H6(0.410989) H15(-0.071213) H10A(0.270575) H10B(0.176837)
 H16(0.042411) H7A(0.694761) H7B(0.750149) H7C(0.76472)
;
_shelx_res_checksum              15464
_shelx_hkl_checksum              70571
_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 3.056
_oxdiff_exptl_absorpt_empirical_full_min 0.484