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_4518546
_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         'C17 H13 N O'
_chemical_formula_sum            'C17 H13 N O'
_chemical_formula_weight         247.28
_space_group_crystal_system      orthorhombic
_space_group_IT_number           41
_space_group_name_Hall           'C -2ac 2'
_space_group_name_H-M_alt        'C 2 e b'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-05-21
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   6.923(3)
_cell_length_b                   21.697(10)
_cell_length_c                   15.616(8)
_cell_measurement_reflns_used    879
_cell_measurement_temperature    273(2)
_cell_measurement_theta_max      24.33
_cell_measurement_theta_min      2.29
_cell_volume                     2345.7(19)
_computing_cell_refinement       'Bruker SMART'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'Bruker SHELXTL'
_computing_structure_solution    'Bruker SHELXTL'
_diffrn_ambient_temperature      273(2)
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0761
_diffrn_reflns_av_unetI/netI     0.1048
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            6928
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.470
_diffrn_reflns_theta_min         2.286
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    0.087
_exptl_absorpt_correction_T_max  0.996
_exptl_absorpt_correction_T_min  0.991
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS v.2.03 (Bruker,200?) was used for absorption correction.
R(int) was 0.1088 before and 0.0687 after correction.
The Ratio of minimum to maximum transmission is 0.5789.
The \l/2 correction factor is 0.0015.
;
_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    1.400
_exptl_crystal_density_meas      1.400
_exptl_crystal_description       block
_exptl_crystal_F_000             1040
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.314
_refine_diff_density_min         -0.291
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Flack x determined using 307 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -5.3(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     228
_refine_ls_number_reflns         2617
_refine_ls_number_restraints     74
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.1445
_refine_ls_R_factor_gt           0.0868
_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^)+(0.1015P)^2^+0.0222P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1951
_refine_ls_wR_factor_ref         0.2354
_reflns_Friedel_coverage         0.804
_reflns_Friedel_fraction_full    0.964
_reflns_Friedel_fraction_max     0.950
_reflns_number_gt                1561
_reflns_number_total             2617
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c00461_si_004.cif
_cod_data_source_block           y0502m
_cod_depositor_comments
'Adding full bibliography for 4518544--4518546.cif.'
_cod_original_cell_volume        2346(2)
_cod_original_sg_symbol_Hall     'C -2bc 2'
_cod_original_sg_symbol_H-M      'C 2 c b'
_cod_database_code               4518546
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.996
_shelx_estimated_absorpt_t_min   0.991
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C9-C21 \\sim C17-C19
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C9A) \\sim Ueq, Uanis(C1AB) \\sim Ueq, Uanis(C19) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C9A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C4AB) \\sim Ueq, Uanis(C5A) \\sim Ueq, Uanis(C3AB) \\sim Ueq, Uanis(C2AB)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C9A) \\sim Ueq, Uanis(C1AA) \\sim Ueq, Uanis(C17) \\sim Ueq: with sigma
of 0.001 and sigma for terminal atoms of 0.002
Uanis(C0AB) \\sim Ueq, Uanis(C21A) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C19A) \\sim Ueq, Uanis(C1AB) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
4. Others
 Sof(C2AB)=Sof(H2AB)=Sof(C3AB)=Sof(H3AB)=Sof(C5A)=Sof(H5A)=Sof(C4AB)=Sof(H4AB)=
 1-FVAR(1)
 Sof(C2AA)=Sof(H2AA)=Sof(C4AA)=Sof(H4AA)=Sof(C5AA)=Sof(H5AA)=Sof(C3AA)=
 Sof(H3AA)=FVAR(1)
 Sof(C9A)=Sof(C0AB)=Sof(H0AB)=Sof(C19A)=Sof(H19A)=Sof(C1AB)=Sof(H1AB)=
 Sof(C17A)=Sof(H17A)=Sof(C21A)=Sof(H21A)=1-FVAR(2)
 Sof(C9)=Sof(C0AA)=Sof(H0AA)=Sof(C1AA)=Sof(H1AA)=Sof(C19)=Sof(H19)=Sof(C17)=
 Sof(H17)=Sof(C21)=Sof(H21)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C11(H11A,H11B)
5.b Aromatic/amide H refined with riding coordinates:
 C2AA(H2AA), C4AA(H4AA), C5AA(H5AA), C3AA(H3AA), C2AB(H2AB), C3AB(H3AB),
 C5A(H5A), C4AB(H4AB), C0AA(H0AA), C1AA(H1AA), C19(H19), C17(H17), C21(H21),
 C0AB(H0AB), C19A(H19A), C1AB(H1AB), C17A(H17A), C21A(H21A)
5.c Fitted hexagon refined as free rotating group:
 C2AA(C8,C4,C4AA,C5AA,C3AA), C9(C0AA,C1AA,C19,C17,C21), C9A(C0AB,C19A,C1AB,
 C17A,C21A)
;
_shelx_res_checksum              94812
_shelx_hkl_checksum              75322
_olex2_submission_special_instructions 'No special instructions were received'