Gold-Catalyzed 1,1-Carboalkoxylation of Oxetane-Ynamides via Exocyclic Metal Carbenes: Divergent and Atom-Economical Synthesis of Tricyclic N-Heterocycles
Qi, Lin-Jun; Shi, Chong-Yang; Chen, Peng-Fei; Li, Long; Fang, Gang; Qian, Peng-Cheng; Deng, Chao; Zhou, Jin-Mei; Ye, Long-Wu; ACS Catalysis 11 (2021) 3679–3686; doi:10.1021/acscatal.1c00461

data_4518544
_publ_section_title
;
 Gold-Catalyzed 1,1-Carboalkoxylation of Oxetane-Ynamides via Exocyclic
 Metal Carbenes: Divergent and Atom-Economical Synthesis of Tricyclic
 N-Heterocycles
;
_journal_issue                   6
_journal_name_full               'ACS Catalysis'
_journal_page_first              3679
_journal_page_last               3686
_journal_paper_doi               10.1021/acscatal.1c00461
_journal_volume                  11
_journal_year                    2021
_chemical_formula_moiety         'C22 H24 Br N O3 S'
_chemical_formula_sum            'C22 H24 Br N O3 S'
_chemical_formula_weight         462.39
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-12-07
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.736(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   22.5321(6)
_cell_length_b                   8.3857(2)
_cell_length_c                   22.2758(5)
_cell_measurement_reflns_used    4115
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.4450
_cell_measurement_theta_min      4.0210
_cell_volume                     4135.28(18)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4741
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -75.00 -48.00   1.00    1.00    --  -40.75 125.00-150.00   27
  2  \w   -100.00 -30.00   1.00    1.00    --  -40.75 -37.00  30.00   70
  3  \w   -113.00 -11.00   1.00    1.00    --  -40.75 -57.00 120.00  102
  4  \w    -72.00 -46.00   1.00    1.00    --  -40.75-166.00-106.00   26
  5  \w     30.00 104.00   1.00    1.00    --  107.31 -94.00 150.00   74
  6  \w     40.00 100.00   1.00    1.00    --  107.31-125.00  30.00   60
  7  \w     78.00 130.00   1.00    1.00    --  107.31 -61.00 -60.00   52
  8  \w     78.00 136.00   1.00    1.00    --  107.31  61.00   0.00   58
  9  \w     52.00 173.00   1.00    1.00    --  107.31  15.00 120.00  121
 10  \w     37.00  80.00   1.00    1.00    --  107.31 -61.00  60.00   43
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0064003000
_diffrn_orient_matrix_UB_12      0.0353968000
_diffrn_orient_matrix_UB_13      -0.0663814000
_diffrn_orient_matrix_UB_21      0.0684556000
_diffrn_orient_matrix_UB_22      -0.0314456000
_diffrn_orient_matrix_UB_23      0.0170062000
_diffrn_orient_matrix_UB_31      -0.0107904000
_diffrn_orient_matrix_UB_32      -0.1774056000
_diffrn_orient_matrix_UB_33      -0.0162588000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0423
_diffrn_reflns_av_unetI/netI     0.0477
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            6973
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.064
_diffrn_reflns_theta_max         67.064
_diffrn_reflns_theta_min         3.994
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.840
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.26287
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.485
_exptl_crystal_description       block
_exptl_crystal_F_000             1904
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.010
_refine_diff_density_min         -0.892
_refine_diff_density_rms         0.124
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     255
_refine_ls_number_reflns         3695
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0524
_refine_ls_R_factor_gt           0.0471
_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^)+(0.0877P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1216
_refine_ls_wR_factor_ref         0.1285
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3294
_reflns_number_total             3695
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c00461_si_002.cif
_cod_data_source_block           exp_7570
_cod_depositor_comments
'Adding full bibliography for 4518544--4518546.cif.'
_cod_original_cell_volume        4135.24(19)
_cod_database_code               4518544
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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 Ternary CH refined with riding coordinates:
 C7(H7)
2.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C14(H14A,H14B), C2(H2A,H2B), C3(H3A,H3B)
2.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C5(H5), C21(H21), C13(H13), C4(H4), C19(H19), C16(H16), C18(H18),
 C12(H12)
2.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C1(H1A,H1B,H1C)
;
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2018-12-07
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.901
_oxdiff_exptl_absorpt_empirical_full_min 0.524