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_4130518
_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         'C17 H16 O'
_chemical_formula_sum            'C17 H16 O'
_chemical_formula_weight         236.30
_space_group_crystal_system      trigonal
_space_group_IT_number           146
_space_group_name_Hall           'R 3'
_space_group_name_H-M_alt        'R 3 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-03-16
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            18
_cell_length_a                   24.0701(6)
_cell_length_b                   24.0701(6)
_cell_length_c                   12.2447(5)
_cell_measurement_reflns_used    7395
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      75.5480
_cell_measurement_theta_min      3.7280
_cell_volume                     6143.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41n (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41n (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41n (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    '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                 'Hybrid Pixel Array Detector'
_diffrn_detector_type            'PILATUS3 R 200K Hybrid Pixel Array Detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -32.00  84.00   1.00    2.00    --    0.00  19.00 150.00  116
  2  \w    -17.00   9.00   1.00    2.00    --    0.00 -82.00-150.00   26
  3  \w    -18.00  15.00   1.00    2.00    --    0.00 -82.00  30.00   33
  4  \w    116.00 188.00   1.00    8.00    --  101.10  30.00 120.00   72
  5  \w    154.00 182.00   1.00    8.00    --  101.10  77.00 -60.00   28
  6  \w    118.00 145.00   1.00    8.00    --  101.10  77.00 -60.00   27
  7  \w    126.00 178.00   1.00    8.00    --  101.10  45.00 -60.00   52
  8  \w     78.00 190.00   1.00    8.00    --  101.10  30.00   0.00  112
  9  \w     80.00 111.00   1.00    8.00    --  101.10  77.00 -60.00   31
 10  \w     82.00 113.00   1.00    8.00    --  101.10  45.00 -60.00   31
 11  \w     66.00 185.00   1.00    8.00    --  101.10  15.00-150.00  119
 12  \w     49.00  74.00   1.00    8.00    --  101.10 -42.00-135.00   25
 13  \w     24.00  68.00   1.00    8.00    --  101.10 -30.00-150.00   44
 14  \w     15.00  51.00   1.00    8.00    --  101.10 -30.00 -90.00   36
 15  \w     17.00 116.00   1.00    8.00    --  101.10 -61.00 -30.00   99
 16  \w     14.00  75.00   1.00    8.00    --  101.10 -45.00 -90.00   61
 17  \w     14.00  66.00   1.00    8.00    --  101.10 -30.00 -30.00   52
 18  \w     22.00  47.00   1.00    8.00    --  101.10 -45.00 -30.00   25
 19  \w     25.00  54.00   1.00    8.00    --  101.10 -30.00   0.00   29
 20  \w     13.00  67.00   1.00    8.00    --  101.10 -30.00 150.00   54
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'XtalLAB PRO MM007, PILATUS3 R 200K'
_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      0.0572621333
_diffrn_orient_matrix_UB_12      0.0553278667
_diffrn_orient_matrix_UB_13      0.0593809667
_diffrn_orient_matrix_UB_21      -0.0171443000
_diffrn_orient_matrix_UB_22      -0.0411183000
_diffrn_orient_matrix_UB_23      0.1044095000
_diffrn_orient_matrix_UB_31      0.0434145333
_diffrn_orient_matrix_UB_32      -0.0265153333
_diffrn_orient_matrix_UB_33      -0.0375398333
_diffrn_radiation_collimation    'VariMax VHF mirror optic'
_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  0.0290
_diffrn_reflns_av_unetI/netI     0.0334
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            14577
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        66.593
_diffrn_reflns_theta_max         66.593
_diffrn_reflns_theta_min         3.673
_diffrn_source                   'rotating anode'
_diffrn_source_current           30
_diffrn_source_power             1.2
_diffrn_source_target            Cu
_diffrn_source_type              'MicroMax 007 HF'
_diffrn_source_voltage           40
_exptl_absorpt_coefficient_mu    0.540
_exptl_absorpt_correction_T_max  0.977
_exptl_absorpt_correction_T_min  0.923
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41n (Rigaku Oxford Diffraction, 2015)
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    1.150
_exptl_crystal_description       plate
_exptl_crystal_F_000             2268
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.148
_exptl_crystal_size_min          0.047
_refine_diff_density_max         0.269
_refine_diff_density_min         -0.137
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 1921 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.16(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     329
_refine_ls_number_reflns         4827
_refine_ls_number_restraints     529
_refine_ls_restrained_S_all      1.113
_refine_ls_R_factor_all          0.0570
_refine_ls_R_factor_gt           0.0521
_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^)+(0.1078P)^2^+1.1138P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1559
_refine_ls_wR_factor_ref         0.1618
_reflns_Friedel_coverage         0.999
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                4242
_reflns_number_total             4827
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b04206_si_005.cif
_cod_data_source_block           cchwle
_cod_original_cell_volume        6143.8(4)
_cod_original_sg_symbol_H-M      'R 3'
_cod_database_code               4130518
_nottingham_internal_coll_name   CCHWLE
_nottingham_internal_coll_number 15765
_nottingham_internal_coll_client CC/HWL
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '2.00, 8.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pczwl
_nottingham_internal_coll_date   01/03/2016
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'XtalLAB PRO, A00000876'
_nottingham_internal_process_date 01/03/2016
_nottingham_internal_process_user pczwl
_nottingham_internal_solution_date 10/3/2016
_nottingham_internal_solution_user pczwl
_nottingham_internal_refinement_date 10/3/2016
_nottingham_internal_refinement_user pczwl
_nottingham_internal_validation_date 16/3/2016
_nottingham_internal_validation_user pczwl
_nottingham_internal_archive_date 16/3/2016
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C17 H16 O'
_chemical_oxdiff_usercomment
'CCHWLE #15765 MM-96 IN FOMBLIN FILM ON MICROMOUNT FOR CC/HWL'
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     67.13
_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. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4.a Ternary CH refined with riding coordinates:
 C1(H1), C21(H21)
4.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C37(H37A,H37B)
4.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C12(H12), C13(H13), C14(H14), C15(H15),
 C16(H16), C25(H25), C26(H26), C27(H27), C28(H28), C32(H32), C33(H33), C34(H34),
  C35(H35), C36(H36)
4.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C38(H38A,H38B,H38C)
4.e Idealised tetrahedral OH refined as rotating group:
 O10(H10), O30(H30)
;
_shelx_res_checksum              21435
_shelx_hkl_checksum              40178
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.542
_oxdiff_exptl_absorpt_empirical_full_min 0.714