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_4036093
_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_formula_moiety         'C26 H23 Br N2 O5 S'
_chemical_formula_sum            'C26 H23 Br N2 O5 S'
_chemical_formula_weight         555.43
_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     dual
_audit_creation_date             2019-03-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                107.572(2)
_cell_angle_beta                 95.879(2)
_cell_angle_gamma                109.928(2)
_cell_formula_units_Z            2
_cell_length_a                   9.7408(2)
_cell_length_b                   10.3272(2)
_cell_length_c                   13.5807(3)
_cell_measurement_reflns_used    12291
_cell_measurement_temperature    99.97(10)
_cell_measurement_theta_max      76.5750
_cell_measurement_theta_min      3.5050
_cell_volume                     1191.86(5)
_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      99.97(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_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   -115.00 -89.00   0.50    0.05    --  -46.62-142.00 -74.00   52
  2  \w    -96.00 -57.00   0.50    0.05    --  -46.62 142.00 -18.00   78
  3  \w   -115.00 -72.00   0.50    0.05    --  -46.62-128.00  96.00   86
  4  \w    -81.00 -54.00   0.50    0.05    --  -46.62 128.00 171.00   54
  5  \w     45.00  86.00   0.50    0.05    --   46.62-128.00  96.00   82
  6  \w     69.00  94.00   0.50    0.05    --   46.62 142.00 -18.00   50
  7  \w     93.00 118.00   0.50    0.05    --   46.62 128.00 171.00   50
  8  \w     40.00  65.00   0.50    0.05    --   46.62-142.00 -74.00   50
  9  \w    -99.00 -61.00   0.50    0.05    -- -100.00-142.00 -74.00   76
 10  \w    -85.00 -49.00   0.50    0.05    -- -100.00 142.00 -18.00   72
 11  \w   -109.00 -42.00   0.50    0.05    -- -100.00 128.00 171.00  134
 12  \w   -121.00 -91.00   0.50    0.05    -- -100.00 142.00 -18.00   60
 13  \w     74.00 129.00   0.50    0.05    --  107.00-142.00 -74.00  110
 14  \w    100.00 126.00   0.50    0.05    --  107.00 142.00 -18.00   52
 15  \w     52.00  77.00   0.50    0.05    --  107.00-128.00  96.00   50
 16  \w     23.00 120.00   0.50    0.05    --   46.62  77.00 150.00  194
 17  \w    -29.00  62.00   0.50    0.05    --   46.62 -19.00-180.00  182
 18  \w     37.00 119.00   0.50    0.05    --   46.62  38.00 -30.00  164
 19  \w   -120.00 -84.00   0.50    0.05    -- -100.00 -15.00-150.00   72
 20  \w   -172.00-141.00   0.50    0.05    -- -100.00 -15.00-150.00   62
 21  \w   -112.00 -82.00   0.50    0.05    -- -100.00  30.00 -90.00   60
 22  \w   -104.00 -62.00   0.50    0.05    -- -100.00  45.00-150.00   84
 23  \w   -176.00 -82.00   0.50    0.05    -- -100.00 -15.00 -60.00  188
 24  \w    -68.00 -25.00   0.50    0.05    -- -100.00  30.00 -90.00   86
 25  \w    -52.00 -27.00   0.50    0.05    -- -100.00  45.00-150.00   50
 26  \w   -110.00 -25.00   0.50    0.05    -- -100.00  30.00 120.00  170
 27  \w   -114.00 -36.00   0.50    0.05    -- -100.00  61.00   0.00  156
 28  \w     77.00 108.00   0.50    0.05    --  107.00 -94.00 -30.00   62
 29  \w     36.00 120.00   0.50    0.05    --  107.00 -45.00-120.00  168
 30  \w     95.00 123.00   0.50    0.05    --  107.00 -61.00  60.00   56
 31  \w     69.00  95.00   0.50    0.05    --  107.00 -94.00   0.00   52
 32  \w     37.00 103.00   0.50    0.05    --  107.00 -94.00  90.00  132
 33  \w     46.00  90.00   0.50    0.05    --  107.00 -61.00  60.00   88
 34  \w    114.00 139.00   0.50    0.05    --  107.00 128.00 171.00   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      0.0940182000
_diffrn_orient_matrix_UB_12      0.1542259000
_diffrn_orient_matrix_UB_13      0.0841237000
_diffrn_orient_matrix_UB_21      0.0248568000
_diffrn_orient_matrix_UB_22      0.0641976000
_diffrn_orient_matrix_UB_23      -0.0884821000
_diffrn_orient_matrix_UB_31      -0.1428690000
_diffrn_orient_matrix_UB_32      0.0320001000
_diffrn_orient_matrix_UB_33      0.0060875000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0357
_diffrn_reflns_av_unetI/netI     0.0278
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            12081
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.058
_diffrn_reflns_theta_max         67.058
_diffrn_reflns_theta_min         3.507
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.522
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65346
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.548
_exptl_crystal_description       block
_exptl_crystal_F_000             568
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.751
_refine_diff_density_min         -0.597
_refine_diff_density_rms         0.071
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     318
_refine_ls_number_reflns         4230
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0361
_refine_ls_R_factor_gt           0.0333
_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^)+(0.0455P)^2^+1.2010P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0850
_refine_ls_wR_factor_ref         0.0866
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4090
_reflns_number_total             4230
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b02350_si_002.cif
_cod_data_source_block           cj_cq_181109
_cod_original_cell_volume        1191.85(5)
_cod_database_code               4036093
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.720
_shelx_estimated_absorpt_t_min   0.418
_reflns_odcompleteness_completeness 99.55
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Riding coordinates:
 N009(H009)
2.b Secondary CH2 refined with riding coordinates:
 C00K(H00A,H00B), C00O(H00C,H00D)
2.c Aromatic/amide H refined with riding coordinates:
 C00F(H00F), C00I(H00I), C00M(H00M), C00N(H00N), C00P(H00P), C00Q(H00Q),
 C00R(H00R), C00T(H00T), C00U(H00U), C00V(H00V), C00W(H00W), C00X(H00X)
2.d Idealised Me refined as rotating group:
 C00Y(H00E,H00G,H00H), C00Z(H00J,H00K,H00L)
;
_shelx_res_checksum              8938
_shelx_hkl_checksum              3391
_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 2.272
_oxdiff_exptl_absorpt_empirical_full_min 0.550