Cp*Co(III)-Catalyzed Dearomative [3 + 2] Spiroannulation of 2-Alkenylphenols with Ynamides via C-H Activation.
Lin, Peng-Peng; Han, Xiang-Lei; Ye, Guo-Hua; Li, Ji-Lin; Li, Qingjiang; Wang, Honggen; The Journal of organic chemistry 84 (2019) 12966–12974; doi:10.1021/acs.joc.9b01750

data_4034070
_publ_section_title
;
 Cp*Co(III)-Catalyzed Dearomative [3 + 2] Spiroannulation of
 2-Alkenylphenols with Ynamides via C-H Activation.
;
_journal_issue                   20
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              12966
_journal_page_last               12974
_journal_paper_doi               10.1021/acs.joc.9b01750
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C23 H27 N O4 S'
_chemical_formula_sum            'C23 H27 N O4 S'
_chemical_formula_weight         413.51
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 115.593(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.6137(3)
_cell_length_b                   9.3076(2)
_cell_length_c                   16.1577(4)
_cell_measurement_reflns_used    19241
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.4680
_cell_measurement_theta_min      3.2600
_cell_volume                     2117.75(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, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.975
_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    -73.00  26.00   0.50    0.15    --  -46.62  83.00-133.00  198
  2  \w    -25.00  73.00   0.50    0.15    --   46.62 -83.00 106.00  196
  3  \w     20.00 120.00   0.50    0.15    --   46.62  83.00-133.00  200
  4  \w   -126.00 -27.00   0.50    0.40    -- -100.00  83.00-133.00  198
  5  \w   -173.00 -73.00   0.50    0.40    -- -100.00 -83.00 106.00  200
  6  \w     81.00 178.00   0.50    0.40    --  107.00  83.00-133.00  194
  7  \w     34.00 134.00   0.50    0.40    --  107.00 -83.00 106.00  200
  8  \w   -119.00 -20.00   0.50    0.15    --  -46.62 -83.00 106.00  198
  9  \w   -119.00 -71.00   0.50    0.15    --  -46.62-125.00-120.00   96
 10  \w     32.00 120.00   0.50    0.15    --   46.62  38.00   0.00  176
 11  \w   -115.00 -25.00   0.50    0.40    -- -100.00  30.00-120.00  180
 12  \w   -115.00 -25.00   0.50    0.40    -- -100.00  30.00  90.00  180
 13  \w   -117.00 -27.00   0.50    0.40    -- -100.00  61.00  90.00  180
 14  \w   -173.00 -76.00   0.50    0.40    -- -100.00 -77.00-180.00  194
 15  \w   -173.00 -81.00   0.50    0.40    -- -100.00 -94.00  90.00  184
 16  \w     35.00 122.00   0.50    0.40    --  107.00 -45.00  90.00  174
 17  \w     34.00 109.00   0.50    0.40    --  107.00 -94.00 -90.00  150
 18  \w     34.00 109.00   0.50    0.40    --  107.00 -94.00  60.00  150
 19  \w     34.00 109.00   0.50    0.40    --  107.00 -94.00-180.00  150
 20  \w     90.00 178.00   0.50    0.40    --  107.00  61.00 -90.00  176
 21  \w     89.00 178.00   0.50    0.40    --  107.00  15.00 -30.00  178
 22  \w     83.00 178.00   0.50    0.40    --  107.00  77.00 -60.00  190
 23  \w     89.00 178.00   0.50    0.40    --  107.00  15.00 -90.00  178
 24  \w     34.00 117.00   0.50    0.40    --  107.00-125.00 120.00  166
 25  \w     92.00 178.00   0.50    0.40    --  107.00  30.00   0.00  172
 26  \w     34.00 109.00   0.50    0.40    --  107.00 -94.00-150.00  150
 27  \w     92.00 178.00   0.50    0.40    --  107.00  30.00  30.00  172
 28  \w     90.00 178.00   0.50    0.40    --  107.00  61.00-180.00  176
 29  \w     93.00 178.00   0.50    0.40    --  107.00  45.00 150.00  170
 30  \w   -119.00 -47.00   0.50    0.15    --  -46.62 -77.00   0.00  144
 31  \w   -119.00 -30.00   0.50    0.15    --  -46.62 -57.00-180.00  178
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0496824000
_diffrn_orient_matrix_UB_12      0.1410636000
_diffrn_orient_matrix_UB_13      0.0456013000
_diffrn_orient_matrix_UB_21      0.0813654000
_diffrn_orient_matrix_UB_22      -0.0333638000
_diffrn_orient_matrix_UB_23      -0.0267720000
_diffrn_orient_matrix_UB_31      -0.0537555000
_diffrn_orient_matrix_UB_32      0.0798553000
_diffrn_orient_matrix_UB_33      -0.0915665000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.2211
_diffrn_reflns_av_unetI/netI     0.0965
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            25386
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.825
_diffrn_reflns_theta_min         3.290
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.595
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.297
_exptl_crystal_description       block
_exptl_crystal_F_000             880
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.933
_refine_diff_density_min         -1.751
_refine_diff_density_rms         0.314
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.587
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     266
_refine_ls_number_reflns         4360
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.587
_refine_ls_R_factor_all          0.1246
_refine_ls_R_factor_gt           0.1133
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3116
_refine_ls_wR_factor_ref         0.3554
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3894
_reflns_number_total             4360
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b01750_si_002.cif
_cod_data_source_block           hanxl_190225_3
_cod_original_cell_volume        2117.75(9)
_cod_database_code               4034070
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.857
_shelx_estimated_absorpt_t_min   0.646
_reflns_odcompleteness_completeness 99.30
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_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:
 C00I(H00A,H00C), C00P(H00S,H00T), C00S(H00W,H00X)
2.b Aromatic/amide H refined with riding coordinates:
 C00B(H00B), C00D(H00D), C00E(H00E), C00F(H00F), C00H(H00H), C00L(H00L),
 C00M(H00M), C00Q(H00U), C00R(H00V)
2.c Idealised Me refined as rotating group:
 C00K(H00G,H00I,H00J), C00N(H00K,H00N,H00O), C00O(H00P,H00Q,H00R), C00T(H00Y,H,
 HA)
;
_shelx_res_checksum              87088
_shelx_hkl_checksum              71731
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 4.587
_oxdiff_exptl_absorpt_empirical_full_min 0.233