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_4518545
_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_absolute_configuration rm
_chemical_formula_moiety         'C20 H20 Br N O3 S'
_chemical_formula_sum            'C20 H20 Br N O3 S'
_chemical_formula_weight         434.34
_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
_audit_creation_date             2020-05-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   8.3815(2)
_cell_length_b                   16.1769(3)
_cell_length_c                   28.5494(6)
_cell_measurement_reflns_used    7681
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.6570
_cell_measurement_theta_min      3.1450
_cell_volume                     3870.92(14)
_computing_cell_refinement       'CrysAlisPro 1.171.40.21a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.21a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.21a (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 0.999
_diffrn_measured_fraction_theta_max 0.953
_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    -60.00  24.00   0.50    0.24    --  -46.81  45.00-134.00  168
  2  \w    -43.00 -16.00   0.50    1.00    --  -88.50  88.00  73.00   54
  3  \w   -104.00 -69.00   0.50    1.00    --  -88.50  88.00  73.00   70
  4  \w     49.00 105.00   0.50    1.00    --  107.94 -96.00-140.00  112
  5  \w   -120.00 -92.00   0.50    0.24    --  -46.81-125.00-120.00   56
  6  \w     41.00  86.00   0.50    0.24    --   46.81-125.00  60.00   90
  7  \w    -98.00 -22.00   0.50    1.00    --  -88.50  45.00-134.00  152
  8  \w     38.00  65.00   0.50    1.00    --  107.94 -94.00-180.00   54
  9  \w     81.00 108.00   0.50    1.00    --  107.94 -94.00 -90.00   54
 10  \w     45.00 108.00   0.50    1.00    --  107.94 -94.00 120.00  126
 11  \w     41.00 111.00   0.50    1.00    --  107.94 -45.00 -30.00  140
;
_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      0.0129338000
_diffrn_orient_matrix_UB_12      0.0455414000
_diffrn_orient_matrix_UB_13      -0.0472595000
_diffrn_orient_matrix_UB_21      -0.1715249000
_diffrn_orient_matrix_UB_22      -0.0263703000
_diffrn_orient_matrix_UB_23      -0.0122317000
_diffrn_orient_matrix_UB_31      -0.0647839000
_diffrn_orient_matrix_UB_32      0.0793409000
_diffrn_orient_matrix_UB_33      0.0230271000
_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     0.0730
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.953
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            14795
_diffrn_reflns_point_group_measured_fraction_full 0.958
_diffrn_reflns_point_group_measured_fraction_max 0.891
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.436
_diffrn_reflns_theta_min         3.096
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.064
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.22424
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.21a (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    1.491
_exptl_crystal_description       block
_exptl_crystal_F_000             1776
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.988
_refine_diff_density_min         -0.726
_refine_diff_density_rms         0.129
_refine_ls_abs_structure_details
;
 Flack x determined using 2442 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.013(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.111
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     473
_refine_ls_number_reflns         7254
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.111
_refine_ls_R_factor_all          0.0602
_refine_ls_R_factor_gt           0.0520
_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^)+(0.1000P)^2^+3.2510P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1380
_refine_ls_wR_factor_ref         0.1704
_reflns_Friedel_coverage         0.665
_reflns_Friedel_fraction_full    0.904
_reflns_Friedel_fraction_max     0.813
_reflns_number_gt                6546
_reflns_number_total             7254
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c00461_si_003.cif
_cod_data_source_block           qlj-20190603-8-4
_cod_depositor_comments
;
Adding full bibliography for 4518544--4518546.cif.

2025-07-30
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_moiety     '2(C20 H20 Br N O3 S)'
_cod_original_formula_sum        'C40 H40 Br2 N2 O6 S2'
_cod_original_formula_units_Z    4
_cod_original_formula_weight     868.68
_cod_database_code               4518545
_shelxl_version_number           2013-2
_reflns_odcompleteness_completeness 99.97
_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:
 C28(H28), C7(H7)
2.b Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B), C30(H30A,H30B), C9(H9A,H9B), C10(H10A,H10B)
2.c Aromatic/amide H refined with riding coordinates:
 C22(H22), C23(H23), C26(H26), C31(H31), C32(H32), C35(H35), C36(H36),
 C37(H37), C38(H38), C1(H1), C2(H2), C6(H6), C11(H11), C12(H12), C15(H15),
 C16(H16), C18(H18), C19(H19)
2.d Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C), C40(H40A,H40B,H40C), C13(H13A,H13B,H13C), C20(H20A,H20B,
 H20C)
;
_shelx_res_checksum              91804
_shelx_hkl_checksum              89548
_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 2.661
_oxdiff_exptl_absorpt_empirical_full_min 0.374