Pd-Catalyzed Decarboxylative Olefination: Stereoselective Synthesis of Polysubstituted Butadienes and Bioactive Macrocyclic Inhibitors.
Song, Bichao; Xie, Peipei; Li, Yingzi; Hao, Jiping; Wang, Lu; Chen, Xiangyang; Xu, Zhongliang; Quan, Haitian; Lou, Li-Guang; Xia, Yuanzhi; Houk, K. N.; Yang, Weibo; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c00078

data_4135010
_publ_section_title
;
 Pd-Catalyzed Decarboxylative Olefination: Stereoselective Synthesis of
 Polysubstituted Butadienes and Bioactive Macrocyclic Inhibitors.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c00078
_journal_year                    2020
_chemical_formula_moiety         'C25 H23 N O4 S'
_chemical_formula_sum            'C25 H23 N O4 S'
_chemical_formula_weight         433.50
_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             2018-08-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.82(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.970(6)
_cell_length_b                   6.974(5)
_cell_length_c                   29.88(2)
_cell_measurement_reflns_used    1615
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      19.786
_cell_measurement_theta_min      2.622
_cell_volume                     2274(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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      296.15
_diffrn_measured_fraction_theta_full 0.963
_diffrn_measured_fraction_theta_max 0.963
_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  0.0868
_diffrn_reflns_av_unetI/netI     0.0832
_diffrn_reflns_Laue_measured_fraction_full 0.963
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            13664
_diffrn_reflns_point_group_measured_fraction_full 0.963
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        25.005
_diffrn_reflns_theta_max         25.005
_diffrn_reflns_theta_min         1.922
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.173
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.5466
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1216 before and 0.0841 after correction. The Ratio of minimum to maximum transmission is 0.7333. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.266
_exptl_crystal_description       block
_exptl_crystal_F_000             912
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.705
_refine_diff_density_min         -0.619
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     270
_refine_ls_number_reflns         3858
_refine_ls_number_restraints     31
_refine_ls_restrained_S_all      1.139
_refine_ls_R_factor_all          0.1428
_refine_ls_R_factor_gt           0.0903
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1824P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2679
_refine_ls_wR_factor_ref         0.3088
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2189
_reflns_number_total             3858
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c00078_si_003.cif
_cod_data_source_block           mo_20180782-jp-413_0m
_cod_database_code               4135010
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.980
_shelx_estimated_absorpt_t_min   0.968
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 C20, C21
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
3. Uiso/Uaniso restraints and constraints
C20 \\sim C21: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
Uanis(C25) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C22)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4.a Aromatic/amide H refined with riding coordinates:
 N1(H1), C14(H14), C15(H15), C12(H12), C9(H9), C5(H5), C25(H25), C24(H24),
 C23(H23), C22(H22), C21(H21), C16(H16), C11(H11), C3(H3), C6(H6), C10(H10),
 C2(H2)
4.b Fitted hexagon refined as free rotating group:
 C20(C25,C24,C23,C22,C21)
4.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C7(H7A,H7B,H7C)
;
_olex2_submission_special_instructions 'No special instructions were received'