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_7128132
_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         'C23 H25 F O'
_chemical_formula_sum            'C23 H25 F O'
_chemical_formula_weight         336.43
_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                 106.5980(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.21190(10)
_cell_length_b                   5.63310(10)
_cell_length_c                   14.27120(10)
_cell_measurement_reflns_used    8202
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      72.7380
_cell_measurement_theta_min      3.7720
_cell_volume                     940.82(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 5.2349
_diffrn_detector_type            'Agilent Diffraction Atlas S2 detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.992
_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  38.00   1.00    2.00    --  -41.70  19.00-180.00   43
  2  \w    -21.00  33.00   1.00    2.00    --  -41.70  38.00-120.00   54
  3  \w     -5.00  38.00   1.00    2.00    --  -41.70  19.00 120.00   43
  4  \w     -5.00  38.00   1.00    2.00    --  -41.70  19.00  30.00   43
  5  \w    -21.00  33.00   1.00    2.00    --  -41.70  38.00  90.00   54
  6  \w    -21.00  33.00   1.00    2.00    --  -41.70  38.00-150.00   54
  7  \w   -116.00 -17.00   1.00    2.00    --  -41.70 -38.00-180.00   99
  8  \w     -5.00  38.00   1.00    2.00    --  -41.70  19.00 150.00   43
  9  \w     10.00  36.00   1.00    2.00    --   41.70  75.00-138.12   26
 10  \w      9.00  42.00   1.00    2.00    --   41.70  79.00 -49.24   33
 11  \w    103.00 178.00   1.00    8.00    --  104.36  77.00   0.00   75
 12  \w     31.00  72.00   1.00    8.00    --  104.36 -45.00 150.00   41
 13  \w     22.00 106.00   1.00    8.00    --  104.36 -94.00  90.00   84
 14  \w     75.00 177.00   1.00    8.00    --  104.36  61.00-150.00  102
 15  \w     32.00  93.00   1.00    8.00    --  104.36 -61.00 120.00   61
 16  \w     74.00 177.00   1.00    8.00    --  104.36  66.00 137.20  103
 17  \w     75.00 177.00   1.00    8.00    --  104.36  61.00-120.00  102
 18  \w     79.00 177.00   1.00    8.00    --  104.36  45.00 -90.00   98
 19  \w     28.00  57.00   1.00    8.00    --  104.36 -30.00  90.00   29
 20  \w     75.00 177.00   1.00    8.00    --  104.36  61.00-180.00  102
 21  \w     79.00 177.00   1.00    8.00    --  104.36  45.00-180.00   98
 22  \w     97.00 178.00   1.00    8.00    --  104.36 125.00  90.00   81
 23  \w     28.00  57.00   1.00    8.00    --  104.36 -30.00-150.00   29
 24  \w     79.00 174.00   1.00    8.00    --  104.36  45.00-150.00   95
 25  \w     83.00 115.00   1.00    8.00    --  104.36  45.00-120.00   32
 26  \w     79.00 117.00   1.00    8.00    --  104.36  45.00 150.00   38
 27  \w     75.00 103.00   1.00    8.00    --  104.36  61.00 150.00   28
 28  \w    153.00 178.00   1.00    8.00    --  104.36  36.00-157.87   25
 29  \w     81.00 108.00   1.00    8.00    --  104.36  36.00-157.87   27
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova, Atlas 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      0.1118356000
_diffrn_orient_matrix_UB_12      0.1081011000
_diffrn_orient_matrix_UB_13      0.0649641000
_diffrn_orient_matrix_UB_21      -0.0583380000
_diffrn_orient_matrix_UB_22      0.0483031000
_diffrn_orient_matrix_UB_23      0.0806148000
_diffrn_orient_matrix_UB_31      0.0376843000
_diffrn_orient_matrix_UB_32      -0.2466393000
_diffrn_orient_matrix_UB_33      0.0442199000
_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  0.0173
_diffrn_reflns_av_unetI/netI     0.0184
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            10485
_diffrn_reflns_point_group_measured_fraction_full 0.976
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.901
_diffrn_reflns_theta_min         3.777
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    0.614
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.657
_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    1.188
_exptl_crystal_description       'rect. Prism'
_exptl_crystal_F_000             360
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: pentane'
_exptl_crystal_size_max          0.611
_exptl_crystal_size_mid          0.079
_exptl_crystal_size_min          0.073
_refine_diff_density_max         0.210
_refine_diff_density_min         -0.165
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 1498 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     257
_refine_ls_number_reflns         3588
_refine_ls_number_restraints     311
_refine_ls_restrained_S_all      1.006
_refine_ls_R_factor_all          0.0290
_refine_ls_R_factor_gt           0.0287
_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^)+(0.0387P)^2^+0.1594P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0719
_refine_ls_wR_factor_ref         0.0722
_reflns_Friedel_coverage         0.747
_reflns_Friedel_fraction_full    0.947
_reflns_Friedel_fraction_max     0.921
_reflns_number_gt                3543
_reflns_number_total             3588
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc01166a2.cif
_cod_data_source_block           smghld
_cod_depositor_comments
'Adding full bibliography for 7128130--7128133.cif.'
_cod_database_code               7128132
_nottingham_internal_coll_name   SMGHLD
_nottingham_internal_coll_number 18636
_nottingham_internal_coll_client SMG/HWL
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '8.00, 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 'GVB, PL13110001'
_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
_nottingham_internal_archive_date 18/05/2020
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C23H25FO
_chemical_oxdiff_usercomment
'SMGHLD #18635 GVB-1778 for SMG/HWL in Fomblin film on a micromount'
_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. Restrained distances
 C8-C3B \\sim C8-C3A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F1A \\sim C2A \\sim C3A \\sim C4A \\sim C5A \\sim C6A \\sim C7A \\sim F1B \\sim
C2B \\sim C3B \\sim C4B \\sim C5B \\sim C6B \\sim C7B: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C4A) = Uanis(C2B)
Uanis(C5A) = Uanis(C7B)
Uanis(C7A) = Uanis(C5B)
Uanis(C6A) = Uanis(C6B)
Uanis(C3A) = Uanis(C3B)
Uanis(C2A) = Uanis(C4B)
4. Rigid body (RIGU) restrains
 F1A, C2A, C3A, C4A, C5A, C6A, C7A, F1B, C2B, C3B, C4B, C5B, C6B, C7B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{F1A, C2A, C3A, C4A, C5A, C6A, C7A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{F1B, C2B, C3B, C4B, C5B, C6B, C7B}
6. Others
 Sof(F1B)=Sof(C2B)=Sof(C3B)=Sof(C4B)=Sof(H4B)=Sof(C5B)=Sof(H5B)=Sof(C6B)=
 Sof(H6B)=Sof(C7B)=Sof(H7B)=1-FVAR(1)
 Sof(F1A)=Sof(C2A)=Sof(C3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=
 Sof(H6A)=Sof(C7A)=Sof(H7A)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C10(H10)
7.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B), C19(H19A,H19B)
7.c Aromatic/amide H refined with riding coordinates:
 C4A(H4A), C5A(H5A), C6A(H6A), C7A(H7A), C14(H14), C15(H15), C16(H16),
 C17(H17), C18(H18), C4B(H4B), C5B(H5B), C6B(H6B), C7B(H7B)
7.d Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              21546
_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 1.439
_oxdiff_exptl_absorpt_empirical_full_min 0.867