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_4515240
_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         'C19 H16.74 N O2'
_chemical_formula_sum            'C19 H17 N O2'
_chemical_formula_weight         291.33
_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   mixed
_audit_creation_date             2019-08-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.463(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.2893(5)
_cell_length_b                   20.9264(18)
_cell_length_c                   11.5081(10)
_cell_measurement_reflns_used    8853
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      27.239
_cell_measurement_theta_min      2.644
_cell_volume                     1498.1(2)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0495
_diffrn_reflns_av_unetI/netI     0.0357
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            23663
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.567
_diffrn_reflns_theta_min         2.644
_exptl_absorpt_coefficient_mu    0.084
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.7008
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1347 before and 0.0632 after correction.
The Ratio of minimum to maximum transmission is 0.9399.
The \l/2 correction factor is Not present.
;
_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    1.292
_exptl_crystal_description       block
_exptl_crystal_F_000             616
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.4
_refine_diff_density_max         0.535
_refine_diff_density_min         -0.560
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     218
_refine_ls_number_reflns         3432
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0889
_refine_ls_R_factor_gt           0.0655
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0702P)^2^+1.3132P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1594
_refine_ls_wR_factor_ref         0.1719
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2620
_reflns_number_total             3432
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b04199_si_003.cif
_cod_data_source_block           b190712c_0m_a
_cod_database_code               4515240
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.967
_shelx_estimated_absorpt_t_min   0.951
_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. Restrained distances
 N1-C8A
 1.51 with sigma of 0.02
 C9-C8A
 1.75 with sigma of 0.005
 C8A-H8AB = C8A-H8AA
 0.95 with sigma of 0.001
3. Rigid bond restraints
 C9, C15
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C10, C9
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Sof(C8A)=Sof(H8AA)=Sof(H8AB)=1-FVAR(1)
 Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H15)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C12(H12)
5.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C17(H17A,H17B)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C10(H10), C11(H11), C13(H13), C14(H14),
 C15(H15)
5.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
;
_olex2_submission_special_instructions 'No special instructions were received'