Divergent Construction of Macrocyclic Alkynes via Catalytic Metal Carbene C(sp2)–H Insertion and the Buchner Reaction
Zeng, Qian; Dong, Kuiyong; Pei, Chao; Dong, Shanliang; Hu, Wenhao; Qiu, Lihua; Xu, Xinfang; ACS Catalysis  (2019) 10773–; doi:10.1021/acscatal.9b04199

data_4515237
_publ_section_title
;
 Divergent Construction of Macrocyclic Alkynes via Catalytic Metal Carbene
 C(sp2)--H Insertion and the Buchner Reaction
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              10773
_journal_paper_doi               10.1021/acscatal.9b04199
_journal_year                    2019
_chemical_formula_moiety         'C18 H15 N O2'
_chemical_formula_sum            'C18 H15 N O2'
_chemical_formula_weight         277.31
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-04-05
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.07.26 svn.r3523 for OlexSys, GUI svn.r5532)
;
_cell_angle_alpha                90
_cell_angle_beta                 106.803(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.4722(7)
_cell_length_b                   10.8657(9)
_cell_length_c                   14.4561(11)
_cell_measurement_reflns_used    2232
_cell_measurement_temperature    293.75(10)
_cell_measurement_theta_max      25.5580
_cell_measurement_theta_min      3.5500
_cell_volume                     1424.3(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      293.75(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4471
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.861
_diffrn_measurement_details
;
  1 omega  -18.00   12.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.4340   80.0000    8.0000 30

  2 omega   41.00   83.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       10.4965   46.0000 -126.0000 42

  3 omega   74.00   99.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       10.4965  178.0000    0.0000 25

  4 omega   47.00   97.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       10.4965  178.0000 -150.0000 50

  5 omega   17.00   51.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       10.4965  -99.0000  -30.0000 34

  6 omega  -25.00   24.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.4340  -99.0000  150.0000 49
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0629242000
_diffrn_orient_matrix_UB_12      -0.0325995000
_diffrn_orient_matrix_UB_13      0.0276859000
_diffrn_orient_matrix_UB_21      0.0463873000
_diffrn_orient_matrix_UB_22      0.0456196000
_diffrn_orient_matrix_UB_23      -0.0108313000
_diffrn_orient_matrix_UB_31      -0.0019521000
_diffrn_orient_matrix_UB_32      0.0334594000
_diffrn_orient_matrix_UB_33      0.0417523000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0361
_diffrn_reflns_av_unetI/netI     0.0435
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.861
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            8600
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.861
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.464
_diffrn_reflns_theta_min         2.926
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.085
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90758
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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    1.293
_exptl_crystal_description       block
_exptl_crystal_F_000             584
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.198
_refine_diff_density_min         -0.195
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     191
_refine_ls_number_reflns         3390
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.1011
_refine_ls_R_factor_gt           0.0543
_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^)+(0.0576P)^2^+0.2261P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1182
_refine_ls_wR_factor_ref         0.1511
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2022
_reflns_number_total             3390
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b04199_si_002.cif
_cod_data_source_block           d190404b
_cod_database_code               4515237
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H O N'
_shelx_estimated_absorpt_t_max   0.983
_shelx_estimated_absorpt_t_min   0.978
_reflns_odcompleteness_completeness 99.74
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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:
 C2(H2A,H2B), C18(H18A,H18B)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C7(H7), C8(H8), C11(H11), C12(H12), C13(H13), C14(H14)
2.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C)
;
_olex2_submission_special_instructions 'No special instructions were received'