Intramolecular β-Alkenylation of Cyclohexanones via Pd-Catalyzed Desaturation-Mediated C(sp3)-H/Alkyne Coupling.
Wang, Chengpeng; Naren, Nevin A.; Zheng, Pengfei; Dong, Guangbin; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c02654

data_4134863
_publ_section_title
;
 Intramolecular \b-Alkenylation of Cyclohexanones via Pd-Catalyzed
 Desaturation-Mediated C(sp3)-H/Alkyne Coupling.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c02654
_journal_year                    2020
_chemical_formula_moiety         'C21 H20 N4 O5'
_chemical_formula_sum            'C21 H20 N4 O5'
_chemical_formula_weight         408.41
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-11-27
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.5110(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.6040(4)
_cell_length_b                   20.0492(8)
_cell_length_c                   12.5383(6)
_cell_measurement_reflns_used    9974
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.80
_cell_measurement_theta_min      2.61
_cell_volume                     1895.11(15)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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    '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 0.996
_diffrn_measurement_device       'three-circle diffractometer'
_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  0.0378
_diffrn_reflns_av_unetI/netI     0.0321
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            33272
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.320
_diffrn_reflns_theta_min         2.610
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.104
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6897
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0642 before and 0.0492 after correction. The Ratio of minimum to maximum transmission is 0.9249. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.431
_exptl_crystal_description       prism
_exptl_crystal_F_000             856
_exptl_crystal_recrystallization_method 'obtained by the solvent evaporation'
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.380
_refine_diff_density_min         -0.306
_refine_diff_density_rms         0.050
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     271
_refine_ls_number_reflns         4706
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0782
_refine_ls_R_factor_gt           0.0485
_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^)+(0.0480P)^2^+1.0080P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1082
_refine_ls_wR_factor_ref         0.1197
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3387
_reflns_number_total             4706
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c02654_si_002.cif
_cod_data_source_block           pengfei
_cod_database_code               4134863
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.998
_shelx_estimated_absorpt_t_min   0.997
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
2.a Ternary CH refined with riding coordinates:
 C11(H11), C10(H10)
2.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C8(H8A,H8B), C12(H12A,H12B), C9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 N3(H3), C21(H21), C2(H2), C5(H5), C6(H6), C15(H15), C17(H17), C20(H20),
 C19(H19), C18(H18)
;
_shelx_res_checksum              75609
_shelx_hkl_checksum              10717
_olex2_exptl_crystal_mounting_method 'mounted with a 20um-loop base'
_olex2_submission_special_instructions 'No special instructions were received'