Leveraging the Halo-Nazarov Cyclization for the Chemodivergent Assembly of Functionalized Haloindenes and Indanones.
Holt, Connor; Alachouzos, Georgios; Frontier, Alison J.; Journal of the American Chemical Society 141 (2019) 5461–5469; doi:10.1021/jacs.9b00198

data_4128370
_publ_section_title
;
 Leveraging the Halo-Nazarov Cyclization for the Chemodivergent Assembly
 of Functionalized Haloindenes and Indanones.
;
_journal_issue                   13
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5461
_journal_page_last               5469
_journal_paper_doi               10.1021/jacs.9b00198
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C19 H19 Br O2'
_chemical_formula_sum            'C19 H19 Br O2'
_chemical_formula_weight         359.25
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'I 2y'
_space_group_name_H-M_alt        'I 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-06-02
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 112.704(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.9455(6)
_cell_length_b                   4.95680(10)
_cell_length_c                   19.3568(7)
_cell_measurement_reflns_used    6356
_cell_measurement_temperature    100.01(12)
_cell_measurement_theta_max      76.4040
_cell_measurement_theta_min      2.9060
_cell_volume                     1588.41(10)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015b)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(12)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.983
_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    -62.00  22.00   0.50    1.95    --  -49.62  57.00 -46.00  168
  2  \w    -60.00 -35.00   0.50    7.79    --  -84.25  38.00 120.00   50
  3  \w    -97.00 -12.00   0.50    7.79    --  -84.25  57.00 -46.00  170
  4  \w   -121.00 -37.00   0.50    1.95    --  -49.62 -57.00 172.00  168
  5  \w    -21.00  62.00   0.50    1.95    --   49.62 -57.00 172.00  166
  6  \w     34.00 101.00   0.50    7.79    --  105.75 -57.00 172.00  134
  7  \w     44.00 115.00   0.50    7.79    --  105.75-125.00  90.00  142
  8  \w     84.00 109.00   0.50    7.79    --  105.75 -99.00   0.00   50
  9  \w     43.00  70.00   0.50    7.79    --  105.75 -19.00 -60.00   54
 10  \w     34.00  73.00   0.50    7.79    --  105.75 -38.00 -60.00   78
 11  \w     37.00  71.00   0.50    7.79    --  105.75 -19.00 -30.00   68
 12  \w     37.00 122.00   0.50    1.95    --   49.62  57.00 -46.00  170
 13  \w    114.00 171.00   0.50    7.79    --  105.75  57.00 -46.00  114
 14  \w     54.00  87.00   0.50    7.79    --  105.75 -99.00-150.00   66
 15  \w     34.00  94.00   0.50    1.95    --   49.62-125.00-180.00  120
 16  \w     36.00  80.00   0.50    7.79    --  105.75 -38.00-180.00   88
 17  \w     35.00  66.00   0.50    7.79    --  105.75 -99.00   0.00   62
 18  \w     37.00  71.00   0.50    7.79    --  105.75 -19.00  60.00   68
 19  \w     45.00 105.00   0.50    7.79    --  105.75 -99.00 150.00  120
 20  \w   -120.00 -71.00   0.50    1.95    --  -49.62-125.00 -30.00   98
 21  \w   -156.00 -71.00   0.50    7.79    --  -84.25 -57.00 172.00  170
 22  \w     42.00  68.00   0.50    1.95    --   49.87  77.00-150.00   52
 23  \w    -28.00  -2.00   0.50    1.95    --  -49.87  19.00-150.00   52
 24  \w     71.00 121.00   0.50    1.95    --   49.87  77.00-150.00  100
 25  \w     39.00  66.00   0.50    7.79    --  105.75 -19.00 120.00   54
 26  \w     36.00  67.00   0.50    7.79    --  105.75 -19.00   0.00   62
 27  \w     34.00  60.00   0.50    7.79    --  105.75 -38.00  90.00   52
 28  \w    106.00 166.00   0.50    7.79    --  105.75  38.00  30.00  120
 29  \w     65.00 109.00   0.50    7.79    --  105.75 -99.00 120.00   88
 30  \w    124.00 160.00   0.50    7.79    --  105.75  38.00 -90.00   72
 31  \w     40.00  66.00   0.50    7.79    --  105.75-125.00 -60.00   52
 32  \w     82.00 116.00   0.50    7.79    --  105.75-125.00 -60.00   68
 33  \w     35.00  73.00   0.50    7.79    --  105.75-125.00-120.00   76
 34  \w     86.00 114.00   0.50    7.79    --  105.75-125.00-120.00   56
 35  \w     38.00  66.00   0.50    7.79    --  105.75 -19.00  90.00   56
 36  \w     43.00  84.00   0.50    7.79    --  105.75-125.00  60.00   82
 37  \w     91.00 116.00   0.50    7.79    --  105.75-125.00  60.00   50
 38  \w     35.00  61.00   0.50    7.79    --  105.75 -99.00 120.00   52
 39  \w     51.00  82.00   0.50    7.79    --  105.75 -99.00  90.00   62
 40  \w     41.00 108.00   0.50    7.79    --  105.75 -99.00 -60.00  134
 41  \w     33.00  58.00   0.50    7.79    --  105.75 -19.00  30.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0426543500
_diffrn_orient_matrix_UB_12      0.2211478500
_diffrn_orient_matrix_UB_13      0.0271386500
_diffrn_orient_matrix_UB_21      -0.0163049000
_diffrn_orient_matrix_UB_22      -0.2048233000
_diffrn_orient_matrix_UB_23      0.0523505000
_diffrn_orient_matrix_UB_31      0.0810735500
_diffrn_orient_matrix_UB_32      0.0753603500
_diffrn_orient_matrix_UB_33      0.0630073500
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0525
_diffrn_reflns_av_unetI/netI     0.0390
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            10664
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         77.585
_diffrn_reflns_theta_min         2.855
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.558
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80687
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.502
_exptl_crystal_description       needle
_exptl_crystal_F_000             736
_exptl_crystal_size_max          0.119
_exptl_crystal_size_mid          0.071
_exptl_crystal_size_min          0.026
_refine_diff_density_max         1.790
_refine_diff_density_min         -0.857
_refine_diff_density_rms         0.129
_refine_ls_abs_structure_details
;
 Flack x determined using 1261 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     201
_refine_ls_number_reflns         3259
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0556
_refine_ls_R_factor_gt           0.0541
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1161P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1409
_refine_ls_wR_factor_ref         0.1428
_reflns_Friedel_coverage         0.742
_reflns_Friedel_fraction_full    0.957
_reflns_Friedel_fraction_max     0.927
_reflns_number_gt                3103
_reflns_number_total             3259
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b00198_si_002.cif
_cod_data_source_block           froga07
_cod_original_cell_volume        1588.41(9)
_cod_database_code               4128370
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C18H19O2Br
_shelx_estimated_absorpt_t_max   0.913
_shelx_estimated_absorpt_t_min   0.677
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     67.62
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C1(H1A)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C15(H15), C17(H17), C18(H18)
2.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C)
2.e Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              15467
_shelx_hkl_checksum              12729
_olex2_submission_original_sample_id froga07
_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 1.868
_oxdiff_exptl_absorpt_empirical_full_min 0.481