Enantioselective Synthesis of Biaryl Atropisomers via Pd/Norbornene-Catalyzed Three-Component Cross-Couplings
Ding, Linlin; Sui, Xianwei; Gu, Zhenhua; ACS Catalysis 8 (2018) 5630–; doi:10.1021/acscatal.8b01037

data_4515642
_publ_section_title
;
 Enantioselective Synthesis of Biaryl Atropisomers via
 Pd/Norbornene-Catalyzed Three-Component Cross-Couplings
;
_journal_issue                   6
_journal_name_full               'ACS Catalysis'
_journal_page_first              5630
_journal_paper_doi               10.1021/acscatal.8b01037
_journal_volume                  8
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H14 Cl4 O3, 0.5(C H2 Cl2)'
_chemical_formula_sum            'C25.5 H15 Cl5 O3'
_chemical_formula_weight         546.62
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-02-08
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.7204(15)
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   11.39996(16)
_cell_length_b                   31.0942(5)
_cell_length_c                   19.9369(3)
_cell_measurement_reflns_used    19913
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.7160
_cell_measurement_theta_min      2.5970
_cell_volume                     7018.53(18)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_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_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.981
_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    -77.00 -37.00   1.00    2.00    --  -41.11 -38.00-150.00   40
  2  \w   -115.00 -24.00   1.00    2.00    --  -41.11 -38.00   0.00   91
  3  \w    -95.00  -5.00   1.00    2.00    --  -41.11 125.00 -90.00   90
  4  \w     85.00 115.00   1.00    2.00    --   41.11  38.00 -60.00   30
  5  \w    101.00 157.00   1.00    8.00    --  107.58 125.00   0.00   56
  6  \w     79.00 169.00   1.00    8.00    --  107.58  30.00   0.00   90
  7  \w    151.00 178.00   1.00    8.00    --  107.58  45.00-180.00   27
  8  \w     91.00 129.00   1.00    8.00    --  107.58 -45.00-180.00   38
  9  \w     47.00  73.00   1.00    8.00    --  107.58 -95.00   0.00   26
 10  \w     84.00 110.00   1.00    8.00    --  107.58 -95.00   0.00   26
 11  \w     42.00 122.00   1.00    8.00    --  107.58-125.00 -60.00   80
 12  \w     30.00  66.00   1.00    8.00    --  107.58 -95.00  30.00   36
 13  \w     35.00 137.00   1.00    8.00    --  107.58 -61.00  30.00  102
 14  \w    140.00 166.00   1.00    8.00    --  107.58 125.00 -30.00   26
 15  \w      2.00  29.00   1.00    2.00    --  -41.23  57.00 -90.00   27
 16  \w    -63.00 -36.00   1.00    2.00    --  -41.23  57.00 150.00   27
 17  \w    -61.00 -28.00   1.00    2.00    --  -41.23  57.00 -90.00   33
 18  \w   -112.00 -15.00   1.00    2.00    --  -41.23 -77.00 150.00   97
 19  \w     31.00 101.00   1.00    8.00    --  107.58 -95.00 -30.00   70
 20  \w     98.00 139.00   1.00    8.00    --  107.58  30.00 150.00   41
 21  \w     92.00 142.00   1.00    8.00    --  107.58  30.00  90.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0528926000
_diffrn_orient_matrix_UB_12      0.0370053000
_diffrn_orient_matrix_UB_13      -0.0453138000
_diffrn_orient_matrix_UB_21      -0.0712854000
_diffrn_orient_matrix_UB_22      -0.0327334000
_diffrn_orient_matrix_UB_23      -0.0462311000
_diffrn_orient_matrix_UB_31      -0.1031214000
_diffrn_orient_matrix_UB_32      0.0036500000
_diffrn_orient_matrix_UB_33      0.0431885000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0488
_diffrn_reflns_av_unetI/netI     0.0658
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            45043
_diffrn_reflns_point_group_measured_fraction_full 0.919
_diffrn_reflns_point_group_measured_fraction_max 0.882
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.938
_diffrn_reflns_theta_min         2.231
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.884
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75653
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
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    1.552
_exptl_crystal_description       block
_exptl_crystal_F_000             3324
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.856
_refine_diff_density_min         -0.461
_refine_diff_density_rms         0.106
_refine_ls_abs_structure_details
;
 Flack x determined using 8471 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.051(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1820
_refine_ls_number_reflns         25124
_refine_ls_number_restraints     8
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0603
_refine_ls_R_factor_gt           0.0559
_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^)+(0.0843P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1435
_refine_ls_wR_factor_ref         0.1488
_reflns_Friedel_coverage         0.765
_reflns_Friedel_fraction_full    0.835
_reflns_Friedel_fraction_max     0.780
_reflns_number_gt                23069
_reflns_number_total             25124
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b01037_si_002.cif
_cod_data_source_block           exp_1255
_cod_original_cell_volume        7018.52(18)
_cod_original_formula_sum        'C25.50 H15 Cl5 O3'
_cod_database_code               4515642
_shelx_shelxl_version_number     2017/1
_reflns_odcompleteness_completeness 99.98
_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
2. Rigid bond restraints
 C05B, O0
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C05B \\sim O0: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004
4. Others
 Sof(H05A)=Sof(O0)=1-FVAR(1)
 Sof(O044)=Sof(H05B)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C02S(H02A,H02C), C038(H03C,H03D), C03C(H03A,H03B), C17(H17A,H17B), C04A(H04A,
 H04B), C05F(H05F,H05G), C05H(H05K,H05L), C05J(H05H,H05J), C05L(H05M,H05N)
5.b Aromatic/amide H refined with riding coordinates:
 C01H(H01H), C01M(H01M), C01O(H01O), C4(H4), C01T(H01T), C01U(H01U), C14(H14),
 C020(H020), C021(H021), C16(H16), C21(H21), C028(H028), C02B(H02B), C02E(H02E),
  C02I(H02I), C02K(H02K), C02M(H02M), C02O(H02O), C02Q(H02Q), C02T(H02T),
 C02Z(H02Z), C031(H031), C033(H033), C034(H034), C035(H035), C036(H036),
 C037(H037), C039(H039), C03B(H03E), C03D(H03F), C03I(H03I), C03J(H03J),
 C03Q(H03Q), C03R(H03R), C03S(H03S), C15(H15), C25(H25), C03Z(H03Z), C041(H041),
  C5(H5), C043(H043), C045(H045), C048(H048), C049(H049), C6(H6), C04C(H04C),
 C04F(H04F), C04G(H04G), C04H(H04H), C04K(H04K), C04L(H04L), C04M(H04M),
 C04N(H04N), C04R(H04R), C9(H9), C04V(H04V), C04W(H04W), C04Y(H04Y), C050(H050),
  C051(H051), C052(H052), C055(H055), C056(H056), C057(H057), C05A(H05E),
 C05B(H05B), C05B(H05A), C05C(H05C), C05D(H05D), C10(H10), C23(H23), C05I(H05I),
  C7(H7)
;
_shelx_res_checksum              79348
_shelx_hkl_checksum              58951
_olex2_date_sample_data_collection 2018-02-07
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.559
_oxdiff_exptl_absorpt_empirical_full_min 0.787