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_4128371
_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         'C21 H22 O2'
_chemical_formula_sum            'C21 H22 O2'
_chemical_formula_weight         306.38
_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
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-10-23
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.24780(10)
_cell_length_b                   9.99840(10)
_cell_length_c                   17.56410(10)
_cell_measurement_reflns_used    40595
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.7070
_cell_measurement_theta_min      5.0350
_cell_volume                     1624.03(3)
_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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_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    -45.00  23.00   0.50    0.05    --  -49.87  19.00-150.00  136
  2  \w    -64.00 -38.00   0.50    0.08    --  -84.25 147.00  -2.00   52
  3  \w    -85.00 -60.00   0.50    0.05    --  -49.87 147.00  -2.00   50
  4  \w    -75.00 -50.00   0.50    0.08    --  -84.25 124.00-168.00   50
  5  \w   -114.00 -75.00   0.50    0.05    --  -49.87 -57.00 120.00   78
  6  \w   -109.00 -55.00   0.50    0.05    --  -49.87-147.00 -52.00  108
  7  \w     63.00  88.00   0.50    0.05    --   49.87-147.00 -52.00   50
  8  \w     88.00 113.00   0.50    0.08    --  105.75-147.00 -52.00   50
  9  \w     71.00 102.00   0.50    0.08    --  105.75 -94.00 -90.00   62
 10  \w     62.00  90.00   0.50    0.08    --  105.75 -94.00 -60.00   56
 11  \w     34.00  75.00   0.50    0.08    --  105.75 -15.00-120.00   82
 12  \w     43.00  68.00   0.50    0.08    --  105.75 -30.00 -90.00   50
 13  \w     36.00  72.00   0.50    0.08    --  105.75 -30.00 -30.00   72
 14  \w     35.00  72.00   0.50    0.08    --  105.75 -30.00  30.00   74
 15  \w     35.00 109.00   0.50    0.08    --  105.75 -94.00 120.00  148
 16  \w     38.00  78.00   0.50    0.08    --  105.75-124.00 112.00   80
 17  \w     35.00  64.00   0.50    0.08    --  105.75 -30.00 120.00   58
 18  \w     35.00  65.00   0.50    0.08    --  105.75 -94.00 -90.00   60
 19  \w     36.00  63.00   0.50    0.08    --  105.75 -30.00-120.00   54
 20  \w    148.00 173.00   0.50    0.08    --  105.75 147.00  -2.00   50
 21  \w     46.00  72.00   0.50    0.05    --   49.87-146.00 -52.00   52
 22  \w   -116.00 -81.00   0.50    0.05    --  -49.87 -22.00-125.92   70
 23  \w    -79.00 -43.00   0.50    0.05    --  -49.87 -38.00 -30.00   72
 24  \w    -70.00 -44.00   0.50    0.05    --  -49.87 -38.00 150.00   52
 25  \w    -71.00 -42.00   0.50    0.05    --  -49.87 -19.00 150.00   58
 26  \w    -77.00 -48.00   0.50    0.05    --  -49.87 -22.00-125.92   58
 27  \w     76.00 114.00   0.50    0.05    --   49.87  77.00-180.00   76
 28  \w     84.00 117.00   0.50    0.05    --   49.87  77.00 -60.00   66
 29  \w     29.00  84.00   0.50    0.05    --   49.87  77.00   0.00  110
 30  \w     96.00 121.00   0.50    0.05    --   49.87  57.00   0.00   50
 31  \w     73.00 120.00   0.50    0.05    --   49.87  77.00  60.00   94
 32  \w     29.00  66.00   0.50    0.05    --   49.87  77.00  60.00   74
 33  \w     42.00  71.00   0.50    0.05    --   49.87  38.00 -30.00   58
 34  \w     29.00  54.00   0.50    0.05    --   49.87  77.00 150.00   50
 35  \w     83.00 108.00   0.50    0.05    --   49.87-146.00 -52.00   50
 36  \w     29.00  68.00   0.50    0.05    --   49.87  77.00-120.00   78
 37  \w     38.00  74.00   0.50    0.05    --   49.87  57.00   0.00   72
 38  \w     33.00  93.00   0.50    0.05    --   49.87-125.00-120.00  120
 39  \w     29.00  60.00   0.50    0.05    --   49.87  77.00-150.00   62
 40  \w     29.00  56.00   0.50    0.05    --   49.87  77.00 -60.00   54
 41  \w     79.00 115.00   0.50    0.05    --   49.87  77.00  90.00   72
 42  \w     31.00  58.00   0.50    0.05    --   49.87  77.00  90.00   54
 43  \w     30.00  59.00   0.50    0.05    --   49.87  77.00-180.00   58
 44  \w     38.00  70.00   0.50    0.05    --   49.87  57.00-180.00   64
 45  \w    -99.00 -63.00   0.50    0.08    --  -84.25 -77.00-120.00   72
 46  \w    -88.00 -63.00   0.50    0.08    --  -84.25 -77.00 -30.00   50
 47  \w   -142.00-116.00   0.50    0.08    --  -84.25 -77.00 -30.00   52
 48  \w    -86.00 -61.00   0.50    0.08    --  -84.25 -82.00 -98.60   50
 49  \w    -88.00 -63.00   0.50    0.08    --  -84.25 -77.00-150.00   50
 50  \w    -87.00 -62.00   0.50    0.08    --  -84.25 -80.00 -70.30   50
 51  \w    -90.00 -64.00   0.50    0.08    --  -84.25 -77.00 120.00   52
 52  \w   -102.00 -61.00   0.50    0.08    --  -84.25 -83.00 145.20   82
 53  \w    -89.00 -63.00   0.50    0.08    --  -84.25 -77.00  30.00   52
 54  \w    -89.00 -63.00   0.50    0.08    --  -84.25 -79.00-136.43   52
 55  \w   -142.00-116.00   0.50    0.08    --  -84.25 -77.00  60.00   52
 56  \w   -142.00-116.00   0.50    0.08    --  -84.25 -80.00 -70.30   52
 57  \w    -88.00 -62.00   0.50    0.08    --  -84.25 -80.00-178.68   52
 58  \w    -96.00 -66.00   0.50    0.08    --  -84.25 -75.00 -43.51   60
 59  \w    -89.00 -63.00   0.50    0.08    --  -84.25 -77.00 -60.00   52
 60  \w    -89.00 -63.00   0.50    0.08    --  -84.25 -77.00 -90.00   52
 61  \w    -89.00 -63.00   0.50    0.08    --  -84.25 -78.00  18.01   52
 62  \w    -91.00 -65.00   0.50    0.08    --  -84.25 -73.00  90.89   52
 63  \w    -89.00 -63.00   0.50    0.08    --  -84.25 -82.00-154.09   52
 64  \w    -91.00 -63.00   0.50    0.08    --  -84.25 -77.00  60.00   56
 65  \w    -91.00 -65.00   0.50    0.08    --  -84.25 -75.00-175.24   52
 66  \w   -134.00-108.00   0.50    0.08    --  -84.25 -82.00-154.09   52
 67  \w   -141.00-115.00   0.50    0.08    --  -84.25 -75.00-175.24   52
 68  \w    -88.00 -63.00   0.50    0.08    --  -84.25 -77.00  90.00   50
 69  \w    -92.00 -66.00   0.50    0.08    --  -84.25 -72.00 -20.54   52
 70  \w    -89.00 -63.00   0.50    0.08    --  -84.25 -78.00 160.58   52
 71  \w    -90.00 -64.00   0.50    0.08    --  -84.25 -77.00   0.00   52
 72  \w     86.00 165.00   0.50    0.08    --  105.75  77.00 150.00  158
 73  \w    142.00 176.00   0.50    0.08    --  105.75  77.00-180.00   68
 74  \w     97.00 158.00   0.50    0.08    --  105.75  61.00-180.00  122
 75  \w     70.00 109.00   0.50    0.08    --  105.75 -94.00-180.00   78
 76  \w     34.00  66.00   0.50    0.08    --  105.75 -94.00-180.00   64
 77  \w     85.00 136.00   0.50    0.08    --  105.75  77.00-180.00  102
 78  \w     94.00 134.00   0.50    0.08    --  105.75  61.00  90.00   80
 79  \w     94.00 162.00   0.50    0.08    --  105.75  61.00 -60.00  136
 80  \w    146.00 177.00   0.50    0.08    --  105.75  77.00  90.00   62
 81  \w     94.00 160.00   0.50    0.08    --  105.75  61.00   0.00  132
 82  \w     87.00 132.00   0.50    0.08    --  105.75  77.00  90.00   90
 83  \w     35.00  92.00   0.50    0.08    --  105.75 -77.00   0.00  114
 84  \w     86.00 140.00   0.50    0.08    --  105.75  77.00  60.00  108
 85  \w     74.00 108.00   0.50    0.08    --  105.75 -94.00   0.00   68
 86  \w     85.00 148.00   0.50    0.08    --  105.75  77.00-150.00  126
 87  \w     36.00  62.00   0.50    0.08    --  105.75 -94.00-120.00   52
 88  \w     40.00  85.00   0.50    0.08    --  105.75 -45.00-150.00   90
 89  \w     69.00 109.00   0.50    0.08    --  105.75 -94.00 150.00   80
 90  \w     34.00  65.00   0.50    0.08    --  105.75 -94.00 150.00   62
 91  \w     36.00  90.00   0.50    0.08    --  105.75 -94.00-150.00  108
 92  \w     42.00 101.00   0.50    0.08    --  105.75 -94.00  60.00  118
 93  \w     92.00 125.00   0.50    0.08    --  105.75  61.00  30.00   66
 94  \w     68.00 115.00   0.50    0.08    --  105.75-125.00   0.00   94
 95  \w    130.00 172.00   0.50    0.08    --  105.75  77.00 -60.00   84
 96  \w     99.00 150.00   0.50    0.08    --  105.75  61.00-150.00  102
 97  \w     85.00 122.00   0.50    0.08    --  105.75  77.00 -60.00   74
 98  \w    141.00 176.00   0.50    0.08    --  105.75  77.00 -90.00   70
 99  \w     86.00 177.00   0.50    0.08    --  105.75  77.00   0.00  182
100  \w     62.00 104.00   0.50    0.08    --  105.75 -94.00  90.00   84
101  \w     95.00 159.00   0.50    0.08    --  105.75  61.00 -90.00  128
102  \w     85.00 137.00   0.50    0.08    --  105.75  77.00 120.00  104
103  \w     90.00 116.00   0.50    0.08    --  105.75  77.00  30.00   52
104  \w     85.00 118.00   0.50    0.08    --  105.75  77.00 -90.00   66
105  \w    135.00 161.00   0.50    0.08    --  105.75  61.00 150.00   52
106  \w    130.00 164.00   0.50    0.08    --  105.75  61.00  30.00   68
107  \w     93.00 120.00   0.50    0.08    --  105.75  61.00 150.00   54
108  \w     95.00 126.00   0.50    0.08    --  105.75  61.00-120.00   62
109  \w    133.00 162.00   0.50    0.08    --  105.75  61.00  60.00   58
110  \w     93.00 118.00   0.50    0.08    --  105.75  61.00  60.00   50
111  \w     92.00 161.00   0.50    0.08    --  105.75  61.00 -30.00  138
112  \w     74.00 107.00   0.50    0.08    --  105.75-125.00  30.00   66
113  \w    148.00 178.00   0.50    0.08    --  105.75  77.00 -30.00   60
114  \w     84.00 109.00   0.50    0.08    --  105.75 -94.00-120.00   50
115  \w    132.00 177.00   0.50    0.08    --  105.75  77.00-120.00   90
116  \w     85.00 111.00   0.50    0.08    --  105.75  77.00-120.00   52
117  \w     87.00 113.00   0.50    0.08    --  105.75  77.00 -30.00   52
118  \w    136.00 162.00   0.50    0.08    --  105.75  61.00  90.00   52
119  \w     35.00  64.00   0.50    0.08    --  105.75 -94.00   0.00   58
;
_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      -0.0726633000
_diffrn_orient_matrix_UB_12      0.0254024000
_diffrn_orient_matrix_UB_13      0.0775992000
_diffrn_orient_matrix_UB_21      -0.1458311000
_diffrn_orient_matrix_UB_22      0.0229436000
_diffrn_orient_matrix_UB_23      -0.0403202000
_diffrn_orient_matrix_UB_31      -0.0344882000
_diffrn_orient_matrix_UB_32      -0.1502474000
_diffrn_orient_matrix_UB_33      0.0069570000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0491
_diffrn_reflns_av_unetI/netI     0.0164
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            54751
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         78.051
_diffrn_reflns_theta_min         5.036
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.618
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83400
_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    1.253
_exptl_crystal_description       block
_exptl_crystal_F_000             656
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.194
_exptl_crystal_size_min          0.183
_refine_diff_density_max         0.153
_refine_diff_density_min         -0.212
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 1432 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     210
_refine_ls_number_reflns         3461
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0294
_refine_ls_R_factor_gt           0.0291
_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^)+(0.0416P)^2^+0.3189P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0744
_refine_ls_wR_factor_ref         0.0750
_reflns_Friedel_coverage         0.733
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.990
_reflns_number_gt                3411
_reflns_number_total             3461
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b00198_si_003.cif
_cod_data_source_block           froch01
_cod_database_code               4128371
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C21H22O2
_shelx_estimated_absorpt_t_max   0.895
_shelx_estimated_absorpt_t_min   0.841
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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 Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C14(H14A,H14B)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C10(H10), C11(H11), C16(H16), C17(H17), C18(H18), C19(H19), C20(H20)
2.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C21(H21A,H21B,H21C)
;
_shelx_res_checksum              16228
_shelx_hkl_checksum              53014
_olex2_submission_original_sample_id froch01
_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 1.428
_oxdiff_exptl_absorpt_empirical_full_min 0.703