Enantioselective nickel-catalyzed <i>anti</i>-arylmetallative cyclizations onto acyclic electron-deficient alkenes.
Gillbard, Simone M.; Green, Harley; Argent, Stephen P.; Lam, Hon Wai; Chemical communications (Cambridge, England) 57 (2021) 4436–4439; doi:10.1039/d1cc01166a

data_7128133
_publ_section_title
;
 Enantioselective nickel-catalyzed <i>anti</i>-arylmetallative
 cyclizations onto acyclic electron-deficient alkenes.
;
_journal_issue                   36
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              4436
_journal_page_last               4439
_journal_paper_doi               10.1039/d1cc01166a
_journal_volume                  57
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H18 O S2'
_chemical_formula_sum            'C21 H18 O S2'
_chemical_formula_weight         350.47
_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     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-05-18
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2020-10-22 deposited with the CCDC.	2021-03-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.4000(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.42830(10)
_cell_length_b                   6.96610(10)
_cell_length_c                   16.5307(2)
_cell_measurement_reflns_used    14030
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      72.4740
_cell_measurement_theta_min      5.3500
_cell_volume                     853.90(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      'N2 gas'
_diffrn_ambient_temperature      120(2)
_diffrn_crystal_treatment        'flash frozen in gaseous N2'
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 4.2207
_diffrn_detector_type            'Agilent Diffraction Titan S2 detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.990
_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     -5.00  36.00   1.00    1.00    --  -41.87  19.00 -30.00   41
  2  \w    -21.00  30.00   1.00    1.00    --  -41.87  38.00  90.00   51
  3  \w     -5.00  36.00   1.00    1.00    --  -41.87  19.00 -60.00   41
  4  \w     17.00 113.00   1.00    1.00    --   41.87  38.00 -60.00   96
  5  \w     17.00 113.00   1.00    1.00    --   41.87  38.00  60.00   96
  6  \w     27.00  95.00   1.00    1.00    --   41.87-125.00 120.00   68
  7  \w     31.00  93.00   1.00    2.00    --  101.44 -61.00  60.00   62
  8  \w     31.00  72.00   1.00    2.00    --  101.44 -45.00 -60.00   41
  9  \w     75.00 171.00   1.00    2.00    --  101.44  61.00  60.00   96
 10  \w     28.00 113.00   1.00    2.00    --  101.44-125.00-180.00   85
 11  \w     31.00  72.00   1.00    2.00    --  101.44 -45.00 120.00   41
 12  \w     75.00 171.00   1.00    2.00    --  101.44  61.00-120.00   96
 13  \w     18.00 107.00   1.00    2.00    --  101.44 -94.00  30.00   89
 14  \w     28.00  57.00   1.00    2.00    --  101.44 -30.00  90.00   29
 15  \w     31.00  72.00   1.00    2.00    --  101.44 -45.00  30.00   41
 16  \w     31.00  93.00   1.00    2.00    --  101.44 -61.00-150.00   62
 17  \w     31.00  72.00   1.00    2.00    --  101.44 -45.00 -90.00   41
 18  \w     28.00  57.00   1.00    2.00    --  101.44 -30.00-120.00   29
 19  \w     28.00 113.00   1.00    2.00    --  101.44-125.00   0.00   85
 20  \w    103.00 176.00   1.00    2.00    --  101.44  77.00-180.00   73
 21  \w    103.00 176.00   1.00    2.00    --  101.44  77.00   0.00   73
 22  \w     77.00 172.00   1.00    2.00    --  101.44  45.00 150.00   95
 23  \w    -21.00  30.00   1.00    1.00    --  -41.87  38.00-150.00   51
 24  \w     27.00  95.00   1.00    1.00    --   41.87-125.00-120.00   68
 25  \w     16.00 112.00   1.00    1.00    --   41.87  57.00 -30.00   96
 26  \w     16.00 112.00   1.00    1.00    --   41.87  57.00-120.00   96
 27  \w     16.00 112.00   1.00    1.00    --   41.87  57.00  90.00   96
 28  \w     16.00 112.00   1.00    1.00    --   41.87  57.00-180.00   96
 29  \w     75.00 175.00   1.00    2.00    --  101.44  30.00 -30.00  100
 30  \w     75.00 171.00   1.00    2.00    --  101.44  61.00 -30.00   96
 31  \w     31.00  93.00   1.00    2.00    --  101.44 -61.00 150.00   62
 32  \w     75.00 171.00   1.00    2.00    --  101.44  61.00 -90.00   96
 33  \w     75.00 171.00   1.00    2.00    --  101.44  61.00  90.00   96
 34  \w     75.00 171.00   1.00    2.00    --  101.44  61.00-180.00   96
 35  \w     75.00 171.00   1.00    2.00    --  101.44  61.00-150.00   96
 36  \w     75.00 171.00   1.00    2.00    --  101.44  61.00  30.00   96
 37  \w     75.00 134.00   1.00    2.00    --  101.44  61.00 120.00   59
 38  \w     75.00 171.00   1.00    2.00    --  101.44  61.00   0.00   96
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova, Titan S2'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1563248000
_diffrn_orient_matrix_UB_12      0.1455131000
_diffrn_orient_matrix_UB_13      0.0018093000
_diffrn_orient_matrix_UB_21      -0.1183373000
_diffrn_orient_matrix_UB_22      0.1480537000
_diffrn_orient_matrix_UB_23      0.0412240000
_diffrn_orient_matrix_UB_31      0.0686549000
_diffrn_orient_matrix_UB_32      -0.0760399000
_diffrn_orient_matrix_UB_33      0.0837898000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0216
_diffrn_reflns_av_unetI/netI     0.0151
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            16193
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.454
_diffrn_reflns_theta_min         5.361
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    2.844
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.302
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
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             368
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: pentane'
_exptl_crystal_size_max          0.348
_exptl_crystal_size_mid          0.234
_exptl_crystal_size_min          0.066
_refine_diff_density_max         0.214
_refine_diff_density_min         -0.252
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 1494 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.002(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     245
_refine_ls_number_reflns         3350
_refine_ls_number_restraints     314
_refine_ls_restrained_S_all      1.007
_refine_ls_R_factor_all          0.0235
_refine_ls_R_factor_gt           0.0233
_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^)+(0.0367P)^2^+0.2682P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0635
_refine_ls_wR_factor_ref         0.0636
_reflns_Friedel_coverage         0.830
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.977
_reflns_number_gt                3332
_reflns_number_total             3350
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc01166a2.cif
_cod_data_source_block           smghle
_cod_depositor_comments
'Adding full bibliography for 7128130--7128133.cif.'
_cod_database_code               7128133
_nottingham_internal_coll_name   SMGHLE
_nottingham_internal_coll_number 18637
_nottingham_internal_coll_client SMG/HWL
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '1.00, 2.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pczspa
_nottingham_internal_coll_date   19/02/2020
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVA, PL13110002'
_nottingham_internal_process_date 19/02/2020
_nottingham_internal_process_user pczspa
_nottingham_internal_solution_date 18/05/2020
_nottingham_internal_solution_user pczspa
_nottingham_internal_refinement_date 18/05/2020
_nottingham_internal_refinement_user pczspa
_nottingham_internal_validation_date 18/05/2020
_nottingham_internal_validation_user pczspa
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C21H18OS2
_chemical_oxdiff_usercomment
'SMGHLE #18637 GVA-1783 for SMG/HWL fomblin micromount'
_shelx_estimated_absorpt_t_max   0.834
_shelx_estimated_absorpt_t_min   0.438
_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, All C(H,H) groups
2. Restrained distances
 C2A-C3A = C4A-C5A
 1.36 with sigma of 0.02
 C3A-C4A
 1.42 with sigma of 0.02
 C5B-C4B = C3B-C2B
 1.36 with sigma of 0.02
 C4B-C3B
 1.42 with sigma of 0.02
 S1A-C2A = S1A-C5A
 1.71 with sigma of 0.02
 S1B-C5B = S1B-C2B
 1.71 with sigma of 0.02
 S1B-C4B = S1B-C3B
 2.54 with sigma of 0.04
 S1A-C3A = S1A-C4A
 2.54 with sigma of 0.04
 C2A-C4A = C3A-C5A
 2.31 with sigma of 0.04
 C5B-C3B = C4B-C2B
 2.31 with sigma of 0.04
 S1B-C4B \\sim S1B-C3B
 with sigma of 0.04
 C2A-C3A \\sim C3A-C4A \\sim C4A-C5A
 with sigma of 0.03
 C2A-C4A \\sim C3A-C5A
 with sigma of 0.04
 S1A-C3A \\sim S1A-C4A
 with sigma of 0.04
 C5B-C4B \\sim C4B-C3B \\sim C3B-C2B
 with sigma of 0.03
 C5B-C3B \\sim C4B-C2B
 with sigma of 0.04
 S1B-C5B \\sim S1B-C2B
 with sigma of 0.02
 S1A-C2A \\sim S1A-C5A
 with sigma of 0.02
 S1B-C2B \\sim S1B-C5B \\sim S1A-C5A \\sim S1A-C2A
 with sigma of 0.02
 C6-C3A \\sim C6-C3B
 with sigma of 0.02
3. Restrained planarity
 S1A, C2A, C3A, C4A, C5A
 with sigma of 0.1
 S1B, C2B, C3B, C4B, C5B
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
S1A \\sim C2A \\sim C3A \\sim C4A \\sim C5A: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
S1B \\sim C2B \\sim C3B \\sim C4B \\sim C5B: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
S1A \\sim C2A \\sim C3A \\sim C4A \\sim C5A \\sim S1B \\sim C2B \\sim C3B \\sim
C4B \\sim C5B: within 2.5A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2.5A
Uanis(C2A) = Uanis(C4B)
Uanis(C3A) = Uanis(C3B)
Uanis(C4A) = Uanis(C2B)
5. Rigid body (RIGU) restrains
 S1B, C2B, C3B, C4B, C5B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S1A, C2A, C3A, C4A, C5A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S1A, C2A, C3A, C4A, C5A, S1B, C2B, C3B, C4B, C5B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
6. Others
 Sof(S1B)=Sof(C2B)=Sof(H2B)=Sof(C3B)=Sof(C4B)=Sof(H4B)=Sof(C5B)=Sof(H5B)=1-
 FVAR(1)
 Sof(S1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=Sof(H5A)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C8(H8)
7.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C17(H17A,H17B)
7.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C22(H22), C23(H23),
 C24(H24), C2A(H2A), C4A(H4A), C5A(H5A), C2B(H2B), C4B(H4B), C5B(H5B)
;
_shelx_res_checksum              9204
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_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 1.458
_oxdiff_exptl_absorpt_empirical_full_min 0.796