Palladium-Catalyzed Trisallylation of Azoles with Alkyne via sequential C(sp2)-H and C(sp3)-H Functionalization
Breit, Bernhard; Zheng, Jun; Hosseini, Fereshteh; Dong, Ya-Xi; Chemical Communications  (2018) –; doi:10.1039/C8CC09165J

data_7122702
_publ_section_title
;
 Palladium-Catalyzed Trisallylation of Azoles with Alkyne via sequential
 C(sp2)-H and C(sp3)-H Functionalization
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C8CC09165J
_journal_year                    2018
_chemical_formula_moiety         'C38 H37 N O'
_chemical_formula_sum            'C38 H37 N O'
_chemical_formula_weight         523.68
_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     dual
_audit_creation_date             2017-12-12
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2017-12-12 deposited with the CCDC.
2018-12-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.112(11)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.211(11)
_cell_length_b                   9.492(8)
_cell_length_c                   22.154(15)
_cell_measurement_reflns_used    8760
_cell_measurement_temperature    100
_cell_measurement_theta_max      26.425
_cell_measurement_theta_min      2.369
_cell_volume                     3073(4)
_computing_cell_refinement       'SAINT V8.38A (Madison, 2016)'
_computing_data_collection       'Bruker APEX2 software'
_computing_data_reduction        'SAINT V8.38A (Madison, 2016)'
_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_temperature      100.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device       'fixed-chi two circle goniometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0415
_diffrn_reflns_av_unetI/netI     0.0348
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            45257
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.008
_diffrn_reflns_theta_min         1.393
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           50
_diffrn_source_type              'Incoatec Mo I\ms'
_diffrn_source_voltage           0.6
_exptl_absorpt_coefficient_mu    0.067
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.6921
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1100 before and 0.0506 after correction. The Ratio of minimum to maximum transmission is 0.9284. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.132
_exptl_crystal_description       block
_exptl_crystal_F_000             1120
_exptl_crystal_recrystallization_method
'The material was recrystallised from hexane by slow evaporation'
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.288
_refine_diff_density_min         -0.230
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     398
_refine_ls_number_reflns         6659
_refine_ls_number_restraints     535
_refine_ls_restrained_S_all      0.982
_refine_ls_R_factor_all          0.0762
_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^)+(0.0575P)^2^+1.1444P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1223
_refine_ls_wR_factor_ref         0.1342
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4841
_reflns_number_total             6659
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc09165j2.cif
_cod_data_source_block           breit_jz_169_0m_a
_cod_database_code               7122702
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.996
_shelx_estimated_absorpt_t_min   0.988
_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
 C31-C35 \\sim C35-C36 \\sim C35-C37 \\sim C35-C38 \\sim C31-C35A \\sim
C35A-C36A \\sim C35A-C37A ~
 C35A-C38A
 with sigma of 0.02
 C36-C37 \\sim C37-C38 \\sim C38-C36 \\sim C36A-C37A \\sim C37A-C38A \\sim
C38A-C36A
 with sigma of 0.04
 C31-C36 \\sim C31-C37 \\sim C31-C38 \\sim C31-C36A \\sim C31-C37A \\sim
C31-C38A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C31 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C35A \\sim C36A \\sim C37A
\\sim C38A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C35) = Uanis(C35A)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{C35, C36, C37, C38} sigma for 1-2: 0.02, 1-3: 0.04
as
{C35A, C36A, C37A, C38A}
6. Others
 Sof(C35A)=Sof(C36A)=Sof(H36D)=Sof(H36E)=Sof(H36F)=Sof(C37A)=Sof(H37D)=
 Sof(H37E)=Sof(H37F)=Sof(C38A)=Sof(H38D)=Sof(H38E)=Sof(H38F)=1-FVAR(1)
 Sof(C35)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C37)=Sof(H37A)=Sof(H37B)=
 Sof(H37C)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=FVAR(1)
7.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C11(H11A,H11B)
7.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C33(H33), C32(H32),
 C30(H30), C27(H27), C26(H26), C25(H25), C24(H24), C23(H23), C22(H22), C21(H21),
  C19(H19), C18(H18), C17(H17), C16(H16), C15(H15), C13(H13), C12(H12)
7.c Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C36A(H36D,H36E,
 H36F), C37A(H37D,H37E,H37F), C38A(H38D,H38E,H38F)
;
_shelx_res_checksum              74407
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems 800'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_special_instructions 'No special instructions were received'