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_4130515
_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         'C25 H22 O2'
_chemical_formula_sum            'C25 H22 O2'
_chemical_formula_weight         354.42
_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                   5.8337(4)
_cell_length_b                   14.6798(10)
_cell_length_c                   20.8894(15)
_cell_measurement_reflns_used    4511
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      76.5110
_cell_measurement_theta_min      5.2060
_cell_volume                     1788.9(2)
_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
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
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)'
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_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 5.1806
_diffrn_detector_type            'Agilent Diffraction Atlas detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_details
;
  1 omega  123.00  167.00   2.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   30.0000  150.0000 22

  2 omega   90.00  174.00   2.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   30.0000   30.0000 42

  3 omega   87.00  135.00   2.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   61.0000  -30.0000 24

  4 omega  118.00  178.00   2.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  111.0000 -180.0000 30

  5 omega   70.00   98.00   2.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -45.0000  -90.0000 14

  6 omega   44.00   72.00   2.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -30.0000    0.0000 14

  7 omega   36.00  116.00   2.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -111.0000  -90.0000 40

  8 omega   38.00   90.00   2.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -30.0000 -150.0000 26

  9 omega   41.00  117.00   2.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       43.1277   77.0000    0.0000 38

 10 omega   60.00   96.00   2.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  178.0000 -180.0000 18

 11 omega   41.00   89.00   2.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -45.0000  120.0000 24

 12 omega   39.00  105.00   2.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -111.0000  120.0000 33

 13 omega    1.00   49.00   2.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       43.1277  -99.0000  -30.0000 24

 14 omega -111.00  -17.00   2.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000  -38.0000   90.0000 47
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova-Duo, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_diffrn_orient_matrix_UB_11      -0.2402609000
_diffrn_orient_matrix_UB_12      0.0410922000
_diffrn_orient_matrix_UB_13      -0.0101914000
_diffrn_orient_matrix_UB_21      0.0197616000
_diffrn_orient_matrix_UB_22      0.0504220000
_diffrn_orient_matrix_UB_23      0.0644159000
_diffrn_orient_matrix_UB_31      0.1078275000
_diffrn_orient_matrix_UB_32      0.0823262000
_diffrn_orient_matrix_UB_33      -0.0344607000
_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  0.0242
_diffrn_reflns_av_unetI/netI     0.0263
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            8896
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.924
_diffrn_reflns_theta_min         5.197
_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    0.642
_exptl_absorpt_correction_T_max  0.894
_exptl_absorpt_correction_T_min  0.727
_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    1.316
_exptl_crystal_description       block
_exptl_crystal_F_000             752
_exptl_crystal_size_max          0.6104
_exptl_crystal_size_mid          0.4891
_exptl_crystal_size_min          0.1907
_refine_diff_density_max         0.160
_refine_diff_density_min         -0.208
_refine_diff_density_rms         0.049
_refine_ls_abs_structure_details
;
 Flack x determined using 1472 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.09(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.110
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     248
_refine_ls_number_reflns         3717
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.110
_refine_ls_R_factor_all          0.0342
_refine_ls_R_factor_gt           0.0330
_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^)+(0.0469P)^2^+0.3117P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0840
_refine_ls_wR_factor_ref         0.0846
_reflns_Friedel_coverage         0.706
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.973
_reflns_number_gt                3629
_reflns_number_total             3717
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b04206_si_003.cif
_cod_data_source_block           cchwlc
_cod_database_code               4130515
_nottingham_internal_coll_name   CCHWLC
_nottingham_internal_coll_number 15238
_nottingham_internal_coll_client CC/HWL
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method 'omega scans'
_nottingham_internal_coll_frame_time 2.0000
_nottingham_internal_coll_frame_width 2.0000
_nottingham_internal_coll_user   pczwl
_nottingham_internal_coll_date   26/10/2015
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'SN, XDA 017/09'
_nottingham_internal_process_date 11/11/2015
_nottingham_internal_process_user pczwl
_nottingham_internal_solution_date 11/11/2015
_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         'C25 H22 O2'
_chemical_oxdiff_usercomment
'CCHWLC #15238 SN-741 IN FOMBLIN FIML ON A MICROMOUNT FOR CC/HWL'
_reflns_odcompleteness_completeness 99.89
_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), C20(H20),
 C21(H21), C22(H22), C23(H23), C25(H25), C26(H26)
2.c Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C)
;
_shelx_res_checksum              59778
_shelx_hkl_checksum              95384
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_olex2_submission_special_instructions 'No special instructions were received'