Enantioselective Nickel-Catalyzed anti-Carbometallative Cyclizations of Alkynyl Electrophiles Enabled by Reversible Alkenylnickel E/Z Isomerization.
Clarke, Christopher; Incerti-Pradillos, Celia A; Lam, Hon Wai; Journal of the American Chemical Society 138 (2016) 8068–8071; doi:10.1021/jacs.6b04206

data_4130516
_publ_section_title
;
 Enantioselective Nickel-Catalyzed anti-Carbometallative Cyclizations of
 Alkynyl Electrophiles Enabled by Reversible Alkenylnickel E/Z
 Isomerization.
;
_journal_issue                   26
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8068
_journal_page_last               8071
_journal_paper_doi               10.1021/jacs.6b04206
_journal_volume                  138
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H19 Cl O2'
_chemical_formula_sum            'C21 H19 Cl O2'
_chemical_formula_weight         338.81
_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   mixed
_audit_creation_date             2016-01-20
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.0546(6)
_cell_length_b                   15.0183(16)
_cell_length_c                   18.7832(19)
_cell_measurement_reflns_used    2926
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      73.7680
_cell_measurement_theta_min      3.7730
_cell_volume                     1708.0(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_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 0.999
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_details
;
  1 omega   61.00  105.00   2.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      103.9498  -94.0000   90.0000 22

  2 omega   47.00   91.00   2.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      103.9498  -30.0000   90.0000 22

  3 omega   47.00   93.00   2.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      103.9498  -45.0000   30.0000 23

  4 omega   43.00   69.00   2.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      103.9498  -30.0000  -30.0000 13

  5 omega   36.00   96.00   2.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      103.9498  -45.0000  -30.0000 30

  6 omega   48.00   96.00   2.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      103.9498  -45.0000  -90.0000 24

  7 omega   37.00  109.00   2.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      103.9498 -125.0000  -30.0000 36

  8 omega   34.00   86.00   2.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      103.9498  -30.0000 -180.0000 26

  9 omega  -26.00   44.00   2.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       43.3101  -38.0000   60.0000 35

 10 omega -114.00  -30.00   2.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.3101  -38.0000 -150.0000 42
;
_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_UB_11      0.0804148000
_diffrn_orient_matrix_UB_12      -0.0269194000
_diffrn_orient_matrix_UB_13      0.0747334000
_diffrn_orient_matrix_UB_21      -0.0699182000
_diffrn_orient_matrix_UB_22      0.0917390000
_diffrn_orient_matrix_UB_23      0.0290278000
_diffrn_orient_matrix_UB_31      -0.2312335000
_diffrn_orient_matrix_UB_32      -0.0372314000
_diffrn_orient_matrix_UB_33      0.0171112000
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_wavelength_determination fundamental
_diffrn_reflns_av_R_equivalents  0.0350
_diffrn_reflns_av_unetI/netI     0.0442
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       3
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            6466
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.208
_diffrn_reflns_theta_min         3.768
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_current           0.8
_diffrn_source_power             0.04
_diffrn_source_target            Cu
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    2.049
_exptl_absorpt_correction_T_max  0.849
_exptl_absorpt_correction_T_min  0.759
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.318
_exptl_crystal_description       block
_exptl_crystal_F_000             712
_exptl_crystal_size_max          0.1916
_exptl_crystal_size_mid          0.1491
_exptl_crystal_size_min          0.0957
_refine_diff_density_max         0.174
_refine_diff_density_min         -0.182
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 1201 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.005(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     221
_refine_ls_number_reflns         3353
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0357
_refine_ls_R_factor_gt           0.0315
_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^)+(0.0346P)^2^+0.1701P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0761
_refine_ls_wR_factor_ref         0.0795
_reflns_Friedel_coverage         0.690
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.940
_reflns_number_gt                3105
_reflns_number_total             3353
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b04206_si_002.cif
_cod_data_source_block           cchwld
_cod_database_code               4130516
_nottingham_internal_coll_name   CCHWLD
_nottingham_internal_coll_number 15463
_nottingham_internal_coll_client CC/HWL
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method 'omega scans'
_nottingham_internal_coll_frame_time '8.0000, 3.0000'
_nottingham_internal_coll_frame_width 2.0000
_nottingham_internal_coll_user   pczwl
_nottingham_internal_coll_date   13/01/2016
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVA, PL13110002'
_nottingham_internal_process_date 14/01/2016
_nottingham_internal_process_user pczwl
_nottingham_internal_solution_date 14/1/2016
_nottingham_internal_solution_user pczwl
_nottingham_internal_refinement_date 14/1/2016
_nottingham_internal_refinement_user pczwl
_nottingham_internal_validation_date 20/1/2016
_nottingham_internal_validation_user pczwl
_nottingham_internal_archive_date 20/1/2016
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C21 H19 O2 Cl'
_chemical_oxdiff_usercomment
'CCHWLD #15463 GVA-795 in fomblin on micromount for CC/HWL'
_reflns_odcompleteness_completeness 99.72
_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, All O(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C7(H7A,H7B)
2.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C18(H18), C19(H19),
 C21(H21), C22(H22)
2.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C)
;
_shelx_res_checksum              63344
_shelx_hkl_checksum              61616
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_olex2_submission_special_instructions 'No special instructions were received'