Pd-Catalyzed Enantioselective Heck Reaction of Aryl Triflates and Alkynes.
Zhu, Chenghao; Chu, Haoke; Li, Gen; Ma, Shengming; Zhang, Junliang; Journal of the American Chemical Society  (2019) –; doi:10.1021/jacs.9b10883

data_4133748
_publ_section_title
;
 Pd-Catalyzed Enantioselective Heck Reaction of Aryl Triflates and
 Alkynes.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b10883
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C48 H54 N O P S'
_chemical_formula_sum            'C48 H54 N O P S'
_chemical_formula_weight         723.95
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-07-03
_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                   10.40830(10)
_cell_length_b                   11.28120(10)
_cell_length_c                   33.5735(2)
_cell_measurement_reflns_used    51015
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.1290
_cell_measurement_theta_min      4.1210
_cell_volume                     3942.14(6)
_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_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_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    -19.00  28.00   1.00    1.00    --    0.00  38.00  30.00   47
  2  \w    -17.00  37.00   1.00    1.00    --    0.00  77.00  90.00   54
  3  \w    -19.00  39.00   1.00    1.00    --    0.00  38.00 -60.00   58
  4  \w    -77.00  21.00   1.00    1.00    --    0.00 -57.00  60.00   98
  5  \w    -30.00   2.00   1.00    1.00    --    0.00  77.00 120.00   32
  6  \w    -19.00  87.00   1.00    1.00    --    0.00  38.00-150.00  106
  7  \w    -61.00  16.00   1.00    1.00    --    0.00 -57.00 150.00   77
  8  \w     19.00  88.00   1.00    1.00    --    0.00  77.00 120.00   69
  9  \w     44.00  70.00   1.00    1.00    --    0.00  77.00  90.00   26
 10  \w     44.00  74.00   1.00    1.00    --    0.00  38.00  30.00   30
 11  \w     44.00  89.00   1.00    1.00    --    0.00  38.00 -60.00   45
 12  \w     34.00  84.00   1.00    1.00    --    0.00  38.00  90.00   50
 13  \w    -16.00  12.00   1.00    1.00    --    0.00  38.00  90.00   28
 14  \w     68.00 181.00   1.00    1.00    --   95.80  69.00  24.65  113
 15  \w     67.00  92.00   1.00    1.00    --   95.80  73.00-133.17   25
 16  \w     70.00 104.00   1.00    1.00    --   95.80  64.00  66.23   34
 17  \w    159.00 185.00   1.00    1.00    --   95.80  78.00  -9.97   26
 18  \w     65.00  91.00   1.00    1.00    --   95.80  78.00  -9.97   26
 19  \w    141.00 166.00   1.00    1.00    --   95.80  74.00 -10.14   25
 20  \w    144.00 176.00   1.00    1.00    --   95.80  58.00 -98.91   32
 21  \w     63.00  88.00   1.00    1.00    --   95.80  81.00-157.01   25
 22  \w     63.00  88.00   1.00    1.00    --   95.80  81.00-103.49   25
 23  \w      6.00 120.00   1.00    1.00    --   95.80 -61.00   0.00  114
 24  \w     40.00  78.00   1.00    1.00    --   95.80 -82.00-180.00   38
 25  \w     82.00 108.00   1.00    1.00    --   95.80 -82.00-180.00   26
 26  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 -90.00   25
 27  \w     56.00 128.00   1.00    1.00    --   95.80 -82.00 -60.00   72
 28  \w     72.00  98.00   1.00    1.00    --   95.80  61.00  90.00   26
 29  \w    106.00 181.00   1.00    1.00    --   95.80  61.00  90.00   75
 30  \w      6.00 125.00   1.00    1.00    --   95.80 -82.00-120.00  119
 31  \w    108.00 141.00   1.00    1.00    --   95.80  82.00 125.09   33
 32  \w     63.00  90.00   1.00    1.00    --   95.80  81.00  99.39   27
 33  \w     65.00  91.00   1.00    1.00    --   95.80  78.00 142.26   26
 34  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 125.09   26
 35  \w     66.00  91.00   1.00    1.00    --   95.80  74.00 -10.14   25
 36  \w     65.00  90.00   1.00    1.00    --   95.80  77.00-120.00   25
 37  \w     63.00  89.00   1.00    1.00    --   95.80  82.00-180.00   26
 38  \w     68.00  93.00   1.00    1.00    --   95.80  68.00 -57.26   25
 39  \w     65.00  93.00   1.00    1.00    --   95.80  77.00 -30.00   28
 40  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 150.00   26
 41  \w     65.00  91.00   1.00    1.00    --   95.80  77.00   0.00   26
 42  \w     96.00 128.00   1.00    1.00    --   95.80  77.00   0.00   32
 43  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  30.00   25
 44  \w     63.00  88.00   1.00    1.00    --   95.80  82.00  60.00   25
 45  \w     19.00  69.00   1.00    1.00    --   95.80 -82.00 150.00   50
 46  \w     82.00 128.00   1.00    1.00    --   95.80 -82.00 150.00   46
 47  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 -60.00   26
 48  \w     63.00  88.00   1.00    1.00    --   95.80  82.00  90.00   25
 49  \w    156.00 184.00   1.00    1.00    --   95.80  82.00  90.00   28
 50  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 120.00   25
 51  \w     75.00 169.00   1.00    1.00    --   95.80  45.00-150.00   94
 52  \w     75.00 101.00   1.00    1.00    --   95.80  45.00 120.00   26
 53  \w     64.00  90.00   1.00    1.00    --   95.80  80.00-112.07   26
 54  \w     67.00  93.00   1.00    1.00    --   95.80  71.00  63.81   26
 55  \w     72.00 123.00   1.00    1.00    --   95.80  61.00-180.00   51
 56  \w     63.00 112.00   1.00    1.00    --   95.80  82.00  30.00   49
 57  \w     64.00  89.00   1.00    1.00    --   95.80  80.00 -48.82   25
 58  \w     71.00 125.00   1.00    1.00    --   95.80  61.00 -90.00   54
 59  \w     71.00 180.00   1.00    1.00    --   95.80  61.00 -60.00  109
 60  \w     63.00  89.00   1.00    1.00    --   95.80  82.00   0.00   26
 61  \w     71.00 145.00   1.00    1.00    --   95.80  61.00   0.00   74
 62  \w     65.00  90.00   1.00    1.00    --   95.80  77.00-180.00   25
 63  \w     71.00 185.00   1.00    1.00    --   95.80  61.00 150.00  114
 64  \w     44.00 127.00   1.00    1.00    --   95.80 -82.00  30.00   83
 65  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  90.00   25
 66  \w      6.00 118.00   1.00    1.00    --   95.80 -82.00 120.00  112
 67  \w     67.00  92.00   1.00    1.00    --   95.80  71.00 123.89   25
 68  \w    108.00 185.00   1.00    1.00    --   95.80  64.00  66.23   77
 69  \w     68.00 182.00   1.00    1.00    --   95.80  68.00 -49.00  114
 70  \w     71.00 133.00   1.00    1.00    --   95.80  58.00 -98.91   62
 71  \w     72.00 177.00   1.00    1.00    --   95.80  57.00-136.40  105
;
_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      -0.0272951000
_diffrn_orient_matrix_UB_12      -0.0791555000
_diffrn_orient_matrix_UB_13      -0.0363926000
_diffrn_orient_matrix_UB_21      -0.0183612000
_diffrn_orient_matrix_UB_22      -0.1074736000
_diffrn_orient_matrix_UB_23      0.0277191000
_diffrn_orient_matrix_UB_31      -0.1444067000
_diffrn_orient_matrix_UB_32      0.0286625000
_diffrn_orient_matrix_UB_33      0.0033778000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0491
_diffrn_reflns_av_unetI/netI     0.0201
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            102954
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.585
_diffrn_reflns_theta_min         4.134
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.388
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56632
_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    1.220
_exptl_crystal_description       block
_exptl_crystal_F_000             1552
_exptl_crystal_size_max          0.39
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.202
_refine_diff_density_min         -0.255
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 3374 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.002(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     472
_refine_ls_number_reflns         8003
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0258
_refine_ls_R_factor_gt           0.0253
_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^)+(0.0292P)^2^+1.1271P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0622
_refine_ls_wR_factor_ref         0.0625
_reflns_Friedel_coverage         0.776
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                7887
_reflns_number_total             8003
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b10883_si_002.cif
_cod_data_source_block           exp_932
_cod_database_code               4133748
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.750
_shelx_estimated_absorpt_t_min   0.614
_reflns_odcompleteness_completeness 99.95
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C7(H7), C1(H1), C19(H19)
2.b Secondary CH2 refined with riding coordinates:
 C48(H48A,H48B), C3(H3A,H3B), C2(H2A,H2B), C4(H4A,H4B), C8(H8A,H8B), C5(H5A,
 H5B), C6(H6A,H6B), C12(H12A,H12B), C10(H10A,H10B), C11(H11A,H11B), C9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 C43(H43), C21(H21), C26(H26), C16(H16), C33(H33), C14(H14), C34(H34),
 C15(H15), C32(H32), C13(H13), C38(H38), C27(H27), C23(H23), C41(H41), C31(H31),
  C22(H22), C39(H39), C28(H28), C40(H40), C29(H29)
2.d Idealised Me refined as rotating group:
 C47(H47A,H47B,H47C), C46(H46A,H46B,H46C), C45(H45A,H45B,H45C)
;
_shelx_res_checksum              1949
_shelx_hkl_checksum              15136
_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 1.889
_oxdiff_exptl_absorpt_empirical_full_min 0.641