Electrochemistry-enabled Rh-catalyzed regioselective [4 + 1] and [4 + 2] cycloaddition of benzoic acid with alkynyl esters/amides
Chiu, Wei-Jung; Sun, Chung-Ming; Green Chemistry 26 (2024) 10996–11002; doi:10.1039/D4GC03753G

data_7249418
_publ_section_title
;
 Electrochemistry-enabled Rh-catalyzed regioselective [4 + 1] and [4 + 2]
 cycloaddition of benzoic acid with alkynyl esters/amides
;
_journal_issue                   21
_journal_name_full               'Green Chemistry'
_journal_page_first              10996
_journal_page_last               11002
_journal_paper_doi               10.1039/D4GC03753G
_journal_volume                  26
_journal_year                    2024
_chemical_formula_moiety         'C20 H22 O4'
_chemical_formula_sum            'C20 H22 O4'
_chemical_formula_weight         326.37
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-03-25
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-03-27 deposited with the CCDC.	2024-10-02 downloaded from the CCDC.
;
_cell_angle_alpha                83.847(2)
_cell_angle_beta                 78.595(2)
_cell_angle_gamma                81.772(2)
_cell_formula_units_Z            2
_cell_length_a                   7.4776(2)
_cell_length_b                   9.1826(2)
_cell_length_c                   12.9115(3)
_cell_measurement_reflns_used    7485
_cell_measurement_temperature    99.98(10)
_cell_measurement_theta_max      72.0950
_cell_measurement_theta_min      3.4880
_cell_volume                     857.25(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.96a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.96a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.96a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.98(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.989
_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     59.00 120.00   0.50    0.05    --   69.38  15.00-180.00  122
  2  \w     39.00 117.00   0.50    0.05    --   69.38  15.00 -90.00  156
  3  \w     37.00 106.00   0.50    0.05    --   56.15  15.00  30.00  138
  4  \w     46.00 126.00   0.50    0.05    --   80.61  15.00 -60.00  160
  5  \w     46.00  71.00   0.50    0.05    --   80.61  15.00  30.00   50
  6  \w     74.00 110.00   0.50    0.05    --   80.61  15.00  30.00   72
  7  \w     73.00 121.00   0.50    0.05    --   80.61  15.00  60.00   96
  8  \w     66.00 107.00   0.50    0.05    --   80.61  15.00 150.00   82
  9  \w     39.00  74.00   0.50    0.05    --   80.61-111.00  30.00   70
 10  \w     68.00  93.00   0.50    0.05    --   80.00-105.00-121.25   50
 11  \w     41.00  67.00   0.50    0.05    --   80.00-105.00-121.25   52
 12  \w     60.00  86.00   0.50    0.05    --   80.61-100.00-146.00   52
 13  \w     54.00  80.00   0.50    0.05    --   69.38-100.00-146.00   52
 14  \w     14.00  53.00   0.50    0.05    --   56.15-100.00-146.00   78
 15  \w     39.00  64.00   0.50    0.05    --   80.61 -95.00-120.00   50
 16  \w     40.00  65.00   0.50    0.05    --   80.61 -95.00 -30.00   50
 17  \w     18.00  51.00   0.50    0.05    --   56.15 -95.00  30.00   66
 18  \w     13.00  41.00   0.50    0.05    --   56.15 -95.00  90.00   56
 19  \w     38.00  66.00   0.50    0.05    --   80.61 -95.00  90.00   56
 20  \w     43.00  88.00   0.50    0.05    --   80.61 -95.00  60.00   90
 21  \w     27.00  57.00   0.50    0.05    --   69.38 -95.00 -90.00   60
 22  \w    -56.00 -30.00   0.50    0.05    --  -59.22 100.00 -42.00   52
 23  \w    -97.00 -70.00   0.50    0.05    --  -81.00 114.00-123.49   54
 24  \w    -97.00 -72.00   0.50    0.05    --  -81.00 116.00 -52.33   50
 25  \w    -66.00 -35.00   0.50    0.05    --  -81.00 114.00-123.49   62
 26  \w    -97.00 -35.00   0.50    0.05    --  -81.00 115.00 -17.34  124
 27  \w    -95.00 -36.00   0.50    0.05    --  -81.00 114.00  70.98  118
 28  \w    -97.00 -39.00   0.50    0.05    --  -81.00 116.00 133.85  116
 29  \w    -98.00 -42.00   0.50    0.05    --  -81.00 118.00  98.49  112
 30  \w    -90.00 -50.00   0.50    0.05    --  -76.67 111.00 150.00   80
 31  \w    -92.00 -43.00   0.50    0.05    --  -76.67 111.00  90.00   98
 32  \w    -79.00 -54.00   0.50    0.05    --  -71.82 100.00 -42.00   50
 33  \w    -77.00 -51.00   0.50    0.05    --  -76.67 100.00 -42.00   52
 34  \w    -88.00 -32.00   0.50    0.05    --  -76.67 111.00 -90.00  112
 35  \w   -126.00 -44.00   0.50    0.05    --  -76.67 -15.00  90.00  164
 36  \w   -115.00 -41.00   0.50    0.05    --  -76.67 -15.00   0.00  148
 37  \w   -112.00 -87.00   0.50    0.05    --  -76.67 -15.00-120.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1178349000
_diffrn_orient_matrix_UB_12      -0.1516670000
_diffrn_orient_matrix_UB_13      -0.0093659000
_diffrn_orient_matrix_UB_21      -0.0244194000
_diffrn_orient_matrix_UB_22      0.0019977000
_diffrn_orient_matrix_UB_23      -0.1158774000
_diffrn_orient_matrix_UB_31      0.1743382000
_diffrn_orient_matrix_UB_32      0.0769395000
_diffrn_orient_matrix_UB_33      -0.0374070000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0318
_diffrn_reflns_av_unetI/netI     0.0226
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            10200
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.068
_diffrn_reflns_theta_max         67.068
_diffrn_reflns_theta_min         3.504
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.707
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91784
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.96a (Rigaku Oxford Diffraction, 2023)
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    1.264
_exptl_crystal_description       block
_exptl_crystal_F_000             348
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.275
_refine_diff_density_min         -0.240
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     219
_refine_ls_number_reflns         3011
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0426
_refine_ls_R_factor_gt           0.0352
_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^)+(0.0438P)^2^+0.3614P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0892
_refine_ls_wR_factor_ref         0.0943
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2797
_reflns_number_total             3011
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4gc03753g2.cif
_cod_data_source_block           240370lt_auto
_cod_depositor_comments
'Adding full bibliography for 7249417--7249418.cif.'
_cod_database_code               7249418
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.866
_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.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B)
2.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C10(H10), C11(H11)
2.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C24(H24A,H24B,H24C)
;
_shelx_res_checksum              62564
_shelx_hkl_checksum              28228
_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 1.482
_oxdiff_exptl_absorpt_empirical_full_min 0.683