Palladium-catalyzed carbene/alkyne metathesis with enynones as carbene precursors: synthesis of fused polyheterocycles.
Zheng, Yang; Bao, Ming; Yao, Ruwei; Qiu, Lihua; Xu, Xinfang; Chemical communications (Cambridge, England) 54 (2018) 350–353; doi:10.1039/c7cc08221e

data_7120939
_publ_section_title
;
 Palladium-catalyzed carbene/alkyne metathesis with enynones as carbene
 precursors: synthesis of fused polyheterocycles.
;
_journal_issue                   4
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              350
_journal_page_last               353
_journal_paper_doi               10.1039/c7cc08221e
_journal_volume                  54
_journal_year                    2018
_chemical_formula_moiety         'C31 H27 Br O7'
_chemical_formula_sum            'C31 H27 Br O7'
_chemical_formula_weight         591.44
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-04-24
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_audit_update_record
;
2017-04-24 deposited with the CCDC.
2017-12-04 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.321(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   20.5026(10)
_cell_length_b                   10.6536(6)
_cell_length_c                   12.2454(7)
_cell_measurement_reflns_used    9909
_cell_measurement_temperature    120
_cell_measurement_theta_max      26.23
_cell_measurement_theta_min      2.53
_cell_volume                     2674.7(3)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      120
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0758
_diffrn_reflns_av_unetI/netI     0.0319
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            67628
_diffrn_reflns_theta_full        26.45
_diffrn_reflns_theta_max         26.45
_diffrn_reflns_theta_min         2.53
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.585
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.5891
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1807 before and 0.0871 after correction.
The Ratio of minimum to maximum transmission is 0.7903.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.469
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             1216
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.403
_refine_diff_density_min         -0.467
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.112
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     372
_refine_ls_number_reflns         5495
_refine_ls_number_restraints     8
_refine_ls_restrained_S_all      1.120
_refine_ls_R_factor_all          0.0707
_refine_ls_R_factor_gt           0.0478
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0354P)^2^+1.9939P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0919
_refine_ls_wR_factor_ref         0.0993
_reflns_number_gt                4246
_reflns_number_total             5495
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c7cc08221e2.cif
_cod_data_source_block           b170417a_0ma_a_a
_cod_depositor_comments          'Adding full bibliography for 7120939.cif.'
_cod_database_code               7120939
_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
 O4-C30 = O4-C30A
 1.4 with sigma of 0.02
 O5-C27 = O5-C27A
 1.4 with sigma of 0.02
 C30-C31 = C30A-C31A
 1.5 with sigma of 0.02
 C27-C28 = C27A-C28A
 1.5 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C27) = Uanis(C27A)
Uanis(C28) = Uanis(C28A)
Uanis(C30) = Uanis(C30A)
Uanis(C31) = Uanis(C31A)
4. Others
 Sof(C27A)=Sof(H27C)=Sof(H27D)=Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=1-FVAR(1)
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=FVAR(1)
 Sof(C30A)=Sof(H30C)=Sof(H30D)=Sof(C31A)=Sof(H31D)=Sof(H31E)=Sof(H31F)=1-FVAR(2)
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C16(H16)
5.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C30(H30A,H30B), C27(H27A,H27B), C27A(H27C,H27D), C30A(H30C,
 H30D)
5.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C12(H12), C2(H2), C10(H10), C11(H11), C4(H4), C1(H1), C5(H5)
5.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C28(H28A,H28B,H28C), C31(H31A,H31B,
 H31C), C28A(H28D,H28E,H28F), C31A(H31D,H31E,H31F)
;
_olex2_submission_special_instructions 'No special instructions were received'