Hydroxy Group-Enabled Highly Regio- and Stereo-selective Hydrocarboxylation of Alkynes
Huang, Chaofan; Qian, Hui; Zhang, Wanli; Ma, Shengming; Chemical Science  (2019) –; doi:10.1039/C8SC05743E

data_1550912
_publ_section_title
;
 Hydroxy Group-Enabled Highly Regio- and Stereo-selective
 Hydrocarboxylation of Alkynes
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C8SC05743E
_journal_year                    2019
_chemical_formula_moiety         'C18 H18 O3'
_chemical_formula_sum            'C18 H18 O3'
_chemical_formula_weight         282.32
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-01-10
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-05-24 deposited with the CCDC.    2019-04-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.95790(10)
_cell_length_b                   12.9023(2)
_cell_length_c                   14.8437(2)
_cell_measurement_reflns_used    9800
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      73.9310
_cell_measurement_theta_min      4.5270
_cell_volume                     1524.08(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_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      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -84.00 -43.00   1.00    1.00    --    0.00 -19.00  60.00   41
  2  \w    -51.00  -6.00   1.00    1.00    --    0.00 -82.00-180.00   45
  3  \w    -89.00 -20.00   1.00    1.00    --    0.00 -38.00-120.00   69
  4  \w     -4.00  22.00   1.00    1.00    --    0.00 -82.00-180.00   26
  5  \w    -22.00  20.00   1.00    1.00    --    0.00 -19.00  60.00   42
  6  \w     15.00  88.00   1.00    1.00    --    0.00  19.00   0.00   73
  7  \w      7.00 116.00   1.00    1.00    --   95.80 -82.00 -30.00  109
  8  \w     47.00 120.00   1.00    1.00    --   95.80 -61.00  90.00   73
  9  \w     75.00 112.00   1.00    1.00    --   95.80  45.00-180.00   37
 10  \w     84.00 112.00   1.00    1.00    --   95.80 -82.00  60.00   28
 11  \w     68.00 126.00   1.00    1.00    --   95.80  15.00 -30.00   58
 12  \w    160.00 185.00   1.00    1.00    --   95.80  15.00 -30.00   25
 13  \w     28.00  84.00   1.00    1.00    --   95.80 -82.00  90.00   56
 14  \w    100.00 127.00   1.00    1.00    --   95.80 -82.00  90.00   27
 15  \w     52.00 113.00   1.00    1.00    --   95.80 -45.00   0.00   61
 16  \w     19.00  44.00   1.00    1.00    --   95.80 -61.00  90.00   25
 17  \w      7.00 101.00   1.00    1.00    --   95.80 -61.00 -30.00   94
 18  \w      7.00 127.00   1.00    1.00    --   95.80 -82.00-180.00  120
 19  \w     62.00 106.00   1.00    1.00    --   95.80 -82.00-120.00   44
 20  \w    100.00 184.00   1.00    1.00    --   95.80  30.00-150.00   84
 21  \w     68.00 185.00   1.00    1.00    --   95.80  15.00 -90.00  117
 22  \w     55.00  83.00   1.00    1.00    --   95.80 -61.00-180.00   28
 23  \w     28.00 101.00   1.00    1.00    --   95.80 -82.00 -90.00   73
 24  \w    123.00 177.00   1.00    1.00    --   95.80  45.00-180.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0343244000
_diffrn_orient_matrix_UB_12      0.1163248000
_diffrn_orient_matrix_UB_13      -0.0143711000
_diffrn_orient_matrix_UB_21      0.1872937000
_diffrn_orient_matrix_UB_22      0.0175561000
_diffrn_orient_matrix_UB_23      -0.0213308000
_diffrn_orient_matrix_UB_31      -0.0348627000
_diffrn_orient_matrix_UB_32      -0.0203794000
_diffrn_orient_matrix_UB_33      -0.1005616000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0285
_diffrn_reflns_av_unetI/netI     0.0179
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            15571
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.075
_diffrn_reflns_theta_max         67.075
_diffrn_reflns_theta_min         4.541
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.667
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70986
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.230
_exptl_crystal_description       block
_exptl_crystal_F_000             600
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.34
_exptl_crystal_size_min          0.33
_refine_diff_density_max         0.157
_refine_diff_density_min         -0.083
_refine_diff_density_rms         0.021
_refine_ls_abs_structure_details
;
 Flack x determined using 1068 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.49(7)
_refine_ls_extinction_coef       0.0040(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     194
_refine_ls_number_reflns         2710
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0288
_refine_ls_R_factor_gt           0.0278
_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^)+(0.0300P)^2^+0.1860P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0691
_refine_ls_wR_factor_ref         0.0696
_reflns_Friedel_coverage         0.721
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                2617
_reflns_number_total             2710
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc05743e2.cif
_cod_data_source_block           exp_206
_cod_database_code               1550912
_shelx_shelxl_version_number     2016/6
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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, All O(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C1(H1A), C2(H2), C3(H3), C4(H4), C5(H5), C8(H8), C11(H11), C12(H12), C13(H13),
  C14(H14), C15(H15)
2.b Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C)
2.c Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              1674
_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 2.053
_oxdiff_exptl_absorpt_empirical_full_min 0.570