Zinc-Catalyzed Alkyne-Carbonyl Metathesis of Ynamides with Isatins: Stereoselective Access to Fully Substituted Alkenes.
Ao, Chaoqun; Yang, Xiaohan; Jia, Shikun; Xu, Xinfang; Yuan, Yanqiu; Zhang, Dan; Hu, Wenhao; The Journal of organic chemistry  (2019) –; doi:10.1021/acs.joc.9b02350

data_4036092
_publ_section_title
;
 Zinc-Catalyzed Alkyne-Carbonyl Metathesis of Ynamides with Isatins:
 Stereoselective Access to Fully Substituted Alkenes.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.9b02350
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H30 N2 O5 S'
_chemical_formula_sum            'C25 H30 N2 O5 S'
_chemical_formula_weight         470.57
_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'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2019-04-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.09340(10)
_cell_length_b                   10.18900(10)
_cell_length_c                   27.8072(2)
_cell_measurement_reflns_used    22223
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.6440
_cell_measurement_theta_min      3.1750
_cell_volume                     2293.08(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_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    -23.00  57.00   0.50    0.05    --   46.62 -42.00 147.00  160
  2  \w   -170.00-128.00   0.50    0.10    -- -100.00 -42.00 147.00   84
  3  \w   -145.00 -88.00   0.50    0.10    -- -100.00-100.00 -67.00  114
  4  \w     86.00 164.00   0.50    0.10    --  107.00  88.00 141.00  156
  5  \w   -114.00 -80.00   0.50    0.05    --  -46.62-125.00 -30.00   68
  6  \w     26.00  94.00   0.50    0.05    --   46.62-125.00  30.00  136
  7  \w   -167.00-102.00   0.50    0.10    -- -100.00 -45.00 120.00  130
  8  \w     43.00 101.00   0.50    0.10    --  107.00 -94.00   0.00  116
  9  \w     47.00  99.00   0.50    0.10    --  107.00 -94.00 -30.00  104
 10  \w    -93.00 -67.00   0.50    0.20    -- -100.00  42.00 -60.00   52
 11  \w   -117.00 -91.00   0.50    0.10    --  -46.62-125.00  90.00   52
 12  \w   -108.00 -81.00   0.50    0.10    --  -46.62-125.00-150.00   54
 13  \w     34.00  66.00   0.50    0.20    --  107.00 -15.00 -30.00   64
 14  \w     72.00 100.00   0.50    0.20    --  107.00 -94.00  60.00   56
 15  \w     35.00  61.00   0.50    0.20    --  107.00 -94.00 -90.00   52
 16  \w     87.00 116.00   0.50    0.20    --  107.00 -15.00 -30.00   58
 17  \w    123.00 173.00   0.50    0.20    --  107.00  77.00   0.00  100
 18  \w     92.00 118.00   0.50    0.20    --  107.00  77.00   0.00   52
 19  \w     43.00  69.00   0.50    0.20    --  107.00 -94.00  60.00   52
 20  \w    100.00 156.00   0.50    0.20    --  107.00  30.00 120.00  112
 21  \w     92.00 117.00   0.50    0.20    --  107.00-125.00-180.00   50
 22  \w     83.00 108.00   0.50    0.20    --  107.00 -94.00 -90.00   50
 23  \w     39.00  71.00   0.50    0.20    --  107.00-125.00-180.00   64
 24  \w   -119.00 -23.00   0.50    0.10    --  -46.62 -77.00-180.00  192
 25  \w   -119.00 -23.00   0.50    0.10    --  -46.62 -77.00 -60.00  192
 26  \w   -120.00 -32.00   0.50    0.10    --  -46.62 -38.00 -60.00  176
 27  \w   -119.00 -30.00   0.50    0.10    --  -46.62 -57.00-150.00  178
 28  \w   -119.00 -23.00   0.50    0.10    --  -46.62 -77.00  60.00  192
 29  \w     92.00 158.00   0.50    0.20    --  107.00  30.00 -30.00  132
 30  \w   -152.00-127.00   0.50    0.20    -- -100.00-100.00 -67.00   50
 31  \w    -93.00 -68.00   0.50    0.20    -- -100.00 100.00  37.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1747203000
_diffrn_orient_matrix_UB_12      0.0155569000
_diffrn_orient_matrix_UB_13      -0.0212583000
_diffrn_orient_matrix_UB_21      0.0479811000
_diffrn_orient_matrix_UB_22      0.1356517000
_diffrn_orient_matrix_UB_23      -0.0200861000
_diffrn_orient_matrix_UB_31      0.0583735000
_diffrn_orient_matrix_UB_32      -0.0648899000
_diffrn_orient_matrix_UB_33      -0.0470585000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0438
_diffrn_reflns_av_unetI/netI     0.0234
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            23210
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.059
_diffrn_reflns_theta_max         67.059
_diffrn_reflns_theta_min         3.179
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.588
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71927
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.363
_exptl_crystal_description       block
_exptl_crystal_F_000             1000
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.358
_refine_diff_density_min         -0.292
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.425(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     306
_refine_ls_number_reflns         4102
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0272
_refine_ls_R_factor_gt           0.0267
_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^)+(0.0443P)^2^+0.4757P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0715
_refine_ls_wR_factor_ref         0.0718
_reflns_Friedel_coverage         0.732
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                4046
_reflns_number_total             4102
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b02350_si_003.cif
_cod_data_source_block           aochq_cq-05-029-down_190318_2
_cod_database_code               4036092
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.857
_shelx_estimated_absorpt_t_min   0.647
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.575(16)
 0.425(16)
2. 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
3.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C16(H16A,H16B), C13(H13A,H13B), C14(H14A,H14B), C19(H19A,
 H19B), C18(H18A,H18B)
3.b Aromatic/amide H refined with riding coordinates:
 C32(H32), C4(H4), C28(H28), C7(H7), C31(H31), C29(H29), C5(H5), C6(H6)
3.c Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C33(H33A,H33B,H33C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              70376
_shelx_hkl_checksum              15560
_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 1.331
_oxdiff_exptl_absorpt_empirical_full_min 0.781