Palladium-Catalyzed Highly Regioselective Hydrocarboxylation of Alkynes with Carbon Dioxide
Xiong, Wenfang; Shi, Fuxing; Cheng, Ruixiang; Zhu, Baiyao; Wang, Lu; Chen, Pengquan; Lou, Hongming; Wu, Wanqing; Qi, Chaorong; Lei, Ming; Jiang, Huanfeng; ACS Catalysis  (2020) 7968–; doi:10.1021/acscatal.0c01687

data_4517839
_publ_section_title
;
 Palladium-Catalyzed Highly Regioselective Hydrocarboxylation of Alkynes
 with Carbon Dioxide
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              7968
_journal_paper_doi               10.1021/acscatal.0c01687
_journal_year                    2020
_chemical_formula_moiety         'C23 H28 O2'
_chemical_formula_sum            'C23 H28 O2'
_chemical_formula_weight         336.45
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2019-07-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                76.398(5)
_cell_angle_beta                 74.831(5)
_cell_angle_gamma                88.404(5)
_cell_formula_units_Z            4
_cell_length_a                   10.0446(7)
_cell_length_b                   12.2899(7)
_cell_length_c                   17.0614(9)
_cell_measurement_reflns_used    5910
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      28.8150
_cell_measurement_theta_min      2.5990
_cell_volume                     1974.5(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -14.00  85.00   1.00    4.00    --   11.74  57.00 -60.00   99
  2  \w    -14.00  78.00   1.00    4.00    --   11.74  77.00  60.00   92
  3  \w      2.00  28.00   1.00    4.00    --   11.74 -99.00 150.00   26
  4  \w    -54.00  36.00   1.00    4.00    --   11.74 -57.00 150.00   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0236627000
_diffrn_orient_matrix_UB_12      -0.0132098000
_diffrn_orient_matrix_UB_13      0.0442360000
_diffrn_orient_matrix_UB_21      -0.0355223000
_diffrn_orient_matrix_UB_22      0.0508563000
_diffrn_orient_matrix_UB_23      -0.0019069000
_diffrn_orient_matrix_UB_31      -0.0594821000
_diffrn_orient_matrix_UB_32      -0.0277418000
_diffrn_orient_matrix_UB_33      -0.0021328000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0309
_diffrn_reflns_av_unetI/netI     0.0522
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            13962
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         2.102
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.070
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75586
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.132
_exptl_crystal_description       block
_exptl_crystal_F_000             728
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.629
_refine_diff_density_min         -0.352
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     515
_refine_ls_number_reflns         6957
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0687
_refine_ls_R_factor_gt           0.0528
_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^)+(0.0593P)^2^+0.5416P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1257
_refine_ls_wR_factor_ref         0.1392
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5422
_reflns_number_total             6957
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c01687_si_002.cif
_cod_data_source_block           0716-3-1
_cod_database_code               4517839
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.992
_shelx_estimated_absorpt_t_min   0.990
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 H1-O1
 0.8 with sigma of 0.02
 H2B-O2B
 0.8 with sigma of 0.02
3. Others
 Sof(C21B)=Sof(H21A)=Sof(H21B)=Sof(H21C)=1-FVAR(1)
 Sof(C01D)=Sof(H01D)=Sof(H01E)=Sof(H01F)=FVAR(1)
 Sof(C1AA)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=1-FVAR(2)
 Sof(C23B)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(2)
 Sof(C01F)=Sof(H01G)=Sof(H01H)=Sof(H01I)=1-FVAR(3)
 Sof(C22B)=Sof(H22A)=Sof(H22B)=Sof(H22C)=FVAR(3)
 Sof(C12B)=Sof(H12A)=Sof(H12B)=Sof(H12C)=1-FVAR(4)
 Sof(C01B)=Sof(H01A)=Sof(H01B)=Sof(H01C)=FVAR(4)
4.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C8(H8), C9(H9), C6(H6), C19B(H19B), C5(H5), C18(H18), C16(H16),
 C19(H19), C5B(H5B), C3B(H3B), C6B(H6B), C15(H15), C15B(H15B), C16B(H16B),
 C18B(H18B), C9B(H9B), C8B(H8B)
4.b Idealised Me refined as rotating group:
 C13(H13D,H13E,H13F), C23(H23D,H23E,H23F), C12(H12D,H12E,H12F), C11(H11D,H11E,
 H11F), C22(H22D,H22E,H22F), C21(H21D,H21E,H21F), C13B(H13A,H13B,H13C),
 C11B(H11A,H11B,H11C), C01B(H01A,H01B,H01C), C23B(H23A,H23B,H23C), C01D(H01D,
 H01E,H01F), C22B(H22A,H22B,H22C), C21B(H21A,H21B,H21C), C1AA(H1AA,H1AB,H1AC),
 C01F(H01G,H01H,H01I), C12B(H12A,H12B,H12C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.697
_oxdiff_exptl_absorpt_empirical_full_min 0.626