Enantioselective nickel-catalyzed arylative and alkenylative intramolecular 1,2-allylations of tethered allene–ketones
Di Sanza, Riccardo; Nguyen, Thi Le Nhon; Iqbal, Naeem; Argent, Stephen P.; Lewis, William; Lam, Hon Wai; Chemical Science 11 (2020) 2401–2406; doi:10.1039/C9SC05246A

data_1557079
_publ_section_title
;
 Enantioselective nickel-catalyzed arylative and alkenylative
 intramolecular 1,2-allylations of tethered allene--ketones
;
_journal_issue                   9
_journal_name_full               'Chemical Science'
_journal_page_first              2401
_journal_page_last               2406
_journal_paper_doi               10.1039/C9SC05246A
_journal_volume                  11
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H23 N O3'
_chemical_formula_sum            'C25 H23 N O3'
_chemical_formula_weight         385.44
_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     iterative
_audit_creation_date             2018-04-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.18 svn.r3501 for OlexSys, GUI svn.r5488)
;
_audit_update_record
;
2019-08-07 deposited with the CCDC.	2020-01-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.5460(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.77764(17)
_cell_length_b                   5.95718(5)
_cell_length_c                   12.86001(11)
_cell_measurement_reflns_used    29868
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      73.9310
_cell_measurement_theta_min      3.4730
_cell_volume                     962.352(18)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (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                 'CCD area detector'
_diffrn_detector_area_resol_mean 4.2207
_diffrn_detector_type            'Agilent Diffraction Titan S2 detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_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    -67.00  27.00   1.00    1.00    --  -42.81  57.00-180.00   94
  2  \w    -50.00  28.00   1.00    1.00    --  -42.81  38.00  90.00   78
  3  \w     12.00 115.00   1.00    1.00    --   42.81  77.00-150.00  103
  4  \w     20.00 113.00   1.00    1.00    --   42.81  38.00 -30.00   93
  5  \w     32.00 121.00   1.00    2.00    --  103.32-125.00   0.00   89
  6  \w     35.00  98.00   1.00    2.00    --  103.32 -45.00-150.00   63
  7  \w     31.00  90.00   1.00    2.00    --  103.32 -30.00  60.00   59
  8  \w     31.00  90.00   1.00    2.00    --  103.32 -30.00  90.00   59
  9  \w     23.00 109.00   1.00    2.00    --  103.32 -95.00 123.00   86
 10  \w     80.00 176.00   1.00    2.00    --  103.32  30.00  30.00   96
 11  \w     67.00 178.00   1.00    2.00    --  103.32  15.00 120.00  111
 12  \w     78.00 173.00   1.00    2.00    --  103.32  61.00 150.00   95
 13  \w     31.00  90.00   1.00    2.00    --  103.32 -30.00-180.00   59
 14  \w     80.00 176.00   1.00    2.00    --  103.32  30.00   0.00   96
 15  \w     31.00  90.00   1.00    2.00    --  103.32 -30.00-150.00   59
 16  \w     22.00 109.00   1.00    2.00    --  103.32 -94.00-150.00   87
 17  \w    -50.00  28.00   1.00    1.00    --  -42.81  38.00   0.00   78
 18  \w    -96.00  -2.00   1.00    1.00    --  -42.81 125.00-150.00   94
 19  \w     12.00 115.00   1.00    1.00    --   42.81  77.00 -30.00  103
 20  \w     19.00 112.00   1.00    1.00    --   42.81  57.00 150.00   93
 21  \w     12.00 115.00   1.00    1.00    --   42.81  77.00  60.00  103
 22  \w     35.00  98.00   1.00    2.00    --  103.32 -45.00 -30.00   63
 23  \w     22.00 109.00   1.00    2.00    --  103.32 -94.00  30.00   87
 24  \w     80.00 176.00   1.00    2.00    --  103.32  30.00-120.00   96
 25  \w     73.00 175.00   1.00    2.00    --  103.32  77.00  30.00  102
 26  \w     73.00 175.00   1.00    2.00    --  103.32  77.00  90.00  102
 27  \w     78.00 173.00   1.00    2.00    --  103.32  61.00-180.00   95
 28  \w     78.00 173.00   1.00    2.00    --  103.32  61.00-120.00   95
 29  \w     78.00 173.00   1.00    2.00    --  103.32  61.00 -60.00   95
 30  \w     73.00 175.00   1.00    2.00    --  103.32  77.00  60.00  102
 31  \w     73.00 175.00   1.00    2.00    --  103.32  77.00 -90.00  102
 32  \w   -113.00 -20.00   1.00    1.00    --  -42.81 -38.00-180.00   93
 33  \w   -112.00 -19.00   1.00    1.00    --  -42.81 -57.00-180.00   93
 34  \w   -117.00 -52.00   1.00    1.00    --  -42.81-157.00-112.00   65
 35  \w     12.00 115.00   1.00    1.00    --   42.81  77.00 -90.00  103
 36  \w     12.00 115.00   1.00    1.00    --   42.81  77.00 120.00  103
 37  \w     73.00 175.00   1.00    2.00    --  103.32  77.00-150.00  102
 38  \w     73.00 175.00   1.00    2.00    --  103.32  77.00-180.00  102
 39  \w     80.00 172.00   1.00    2.00    --  103.32  45.00 150.00   92
 40  \w     78.00 173.00   1.00    2.00    --  103.32  61.00   0.00   95
 41  \w     73.00 175.00   1.00    2.00    --  103.32  77.00-120.00  102
 42  \w     78.00 173.00   1.00    2.00    --  103.32  61.00 -30.00   95
 43  \w     73.00 175.00   1.00    2.00    --  103.32  77.00 150.00  102
 44  \w     78.00 173.00   1.00    2.00    --  103.32  61.00  90.00   95
 45  \w     78.00 173.00   1.00    2.00    --  103.32  61.00  30.00   95
 46  \w     73.00 175.00   1.00    2.00    --  103.32  77.00   0.00  102
 47  \w    -32.00 117.00   1.00    1.00    --   42.81   0.00 -60.00  149
 48  \w    -32.00 117.00   1.00    1.00    --   42.81   0.00 -90.00  149
 49  \w    -32.00 117.00   1.00    1.00    --   42.81   0.00-180.00  149
 50  \w    -32.00 117.00   1.00    1.00    --   42.81   0.00-120.00  149
 51  \w    -32.00 117.00   1.00    1.00    --   42.81   0.00-150.00  149
 52  \w     73.00 175.00   1.00    2.00    --  103.32  77.00 -60.00  102
 53  \w     78.00 173.00   1.00    2.00    --  103.32  61.00 120.00   95
 54  \w     78.00 173.00   1.00    2.00    --  103.32  61.00  60.00   95
 55  \w     78.00 173.00   1.00    2.00    --  103.32  61.00-150.00   95
 56  \w     73.00 175.00   1.00    2.00    --  103.32  77.00 -30.00  102
 57  \w     78.00 173.00   1.00    2.00    --  103.32  61.00 -90.00   95
 58  \w     34.00 129.00   1.00    2.00    --  103.32 -61.00 -30.00   95
 59  \w     80.00 172.00   1.00    2.00    --  103.32  45.00-150.00   92
 60  \w     80.00 172.00   1.00    2.00    --  103.32  45.00 -90.00   92
 61  \w     73.00 175.00   1.00    2.00    --  103.32  77.00 120.00  102
 62  \w    -32.00 117.00   1.00    1.00    --   42.81   0.00  90.00  149
 63  \w    -32.00 117.00   1.00    1.00    --   42.81   0.00  60.00  149
 64  \w    -32.00 117.00   1.00    1.00    --   42.81   0.00 -30.00  149
 65  \w    -32.00 117.00   1.00    1.00    --   42.81   0.00  30.00  149
 66  \w    -32.00 117.00   1.00    1.00    --   42.81   0.00   0.00  149
 67  \w     80.00 172.00   1.00    2.00    --  103.32  45.00-120.00   92
 68  \w     29.00 178.00   1.00    2.00    --  103.32   0.00-180.00  149
 69  \w     80.00 172.00   1.00    2.00    --  103.32  45.00   0.00   92
 70  \w     80.00 172.00   1.00    2.00    --  103.32  45.00 120.00   92
 71  \w     80.00 172.00   1.00    2.00    --  103.32  45.00  90.00   92
 72  \w     80.00 172.00   1.00    2.00    --  103.32  45.00  60.00   92
 73  \w     29.00 178.00   1.00    2.00    --  103.32   0.00-150.00  149
 74  \w     29.00 178.00   1.00    2.00    --  103.32   0.00-120.00  149
 75  \w     29.00 178.00   1.00    2.00    --  103.32   0.00 -90.00  149
 76  \w     80.00 172.00   1.00    2.00    --  103.32  45.00  30.00   92
 77  \w   -117.00  32.00   1.00    1.00    --  -42.81   0.00-180.00  149
 78  \w   -117.00  32.00   1.00    1.00    --  -42.81   0.00-150.00  149
 79  \w   -117.00  32.00   1.00    1.00    --  -42.81   0.00-120.00  149
 80  \w    -32.00 117.00   1.00    1.00    --   42.81   0.00 150.00  149
 81  \w    -32.00 117.00   1.00    1.00    --   42.81   0.00 120.00  149
 82  \w     29.00 178.00   1.00    2.00    --  103.32   0.00 -30.00  149
 83  \w     29.00 178.00   1.00    2.00    --  103.32   0.00 120.00  149
 84  \w     29.00 178.00   1.00    2.00    --  103.32   0.00 -60.00  149
 85  \w     29.00 178.00   1.00    2.00    --  103.32   0.00  90.00  149
 86  \w     29.00 178.00   1.00    2.00    --  103.32   0.00  60.00  149
 87  \w     29.00 178.00   1.00    2.00    --  103.32   0.00  30.00  149
 88  \w     29.00 178.00   1.00    2.00    --  103.32   0.00 150.00  149
 89  \w     29.00 178.00   1.00    2.00    --  103.32   0.00-180.00  149
 90  \w     29.00 178.00   1.00    2.00    --  103.32   0.00-150.00  149
 91  \w     29.00 178.00   1.00    2.00    --  103.32   0.00   0.00  149
 92  \w   -117.00  32.00   1.00    1.00    --  -42.81   0.00  30.00  149
 93  \w   -117.00  32.00   1.00    1.00    --  -42.81   0.00   0.00  149
 94  \w   -117.00  32.00   1.00    1.00    --  -42.81   0.00 -90.00  149
 95  \w   -117.00  32.00   1.00    1.00    --  -42.81   0.00 -30.00  149
 96  \w   -117.00  32.00   1.00    1.00    --  -42.81   0.00 -60.00  149
 97  \w     29.00 178.00   1.00    2.00    --  103.32   0.00 -90.00  149
 98  \w     29.00 178.00   1.00    2.00    --  103.32   0.00  60.00  149
 99  \w     29.00 178.00   1.00    2.00    --  103.32   0.00-120.00  149
100  \w     29.00 178.00   1.00    2.00    --  103.32   0.00  30.00  149
101  \w     29.00 178.00   1.00    2.00    --  103.32   0.00   0.00  149
102  \w     29.00 178.00   1.00    2.00    --  103.32   0.00 -30.00  149
103  \w     29.00 178.00   1.00    2.00    --  103.32   0.00  90.00  149
104  \w     29.00 178.00   1.00    2.00    --  103.32   0.00 120.00  149
105  \w     29.00 178.00   1.00    2.00    --  103.32   0.00 150.00  149
106  \w     29.00 178.00   1.00    2.00    --  103.32   0.00 -60.00  149
107  \w   -117.00  32.00   1.00    1.00    --  -42.81   0.00  90.00  149
108  \w   -117.00  32.00   1.00    1.00    --  -42.81   0.00 150.00  149
109  \w   -117.00  32.00   1.00    1.00    --  -42.81   0.00  60.00  149
110  \w   -117.00  32.00   1.00    1.00    --  -42.81   0.00 120.00  149
111  \w    -25.00  80.00   1.00    1.00    --   42.81 -95.00 123.00  105
112  \w     51.00 166.00   1.00    2.00    --  103.32 157.00 -76.00  115
113  \w     26.00 139.00   1.00    2.00    --  103.32 -15.00 -60.00  113
114  \w     51.00 166.00   1.00    2.00    --  103.32 157.00 -76.00  115
115  \w     26.00 139.00   1.00    2.00    --  103.32 -15.00 -90.00  113
116  \w     26.00 139.00   1.00    2.00    --  103.32 -15.00-120.00  113
117  \w     26.00 139.00   1.00    2.00    --  103.32 -15.00-150.00  113
118  \w     26.00 139.00   1.00    2.00    --  103.32 -15.00 -30.00  113
119  \w     26.00 139.00   1.00    2.00    --  103.32 -15.00   0.00  113
120  \w     26.00 139.00   1.00    2.00    --  103.32 -15.00  30.00  113
121  \w     26.00 139.00   1.00    2.00    --  103.32 -15.00-180.00  113
122  \w    -80.00  25.00   1.00    1.00    --  -42.81  95.00-127.00  105
123  \w    -80.00  25.00   1.00    1.00    --  -42.81  95.00-127.00  105
124  \w    -80.00  25.00   1.00    1.00    --  -42.81  95.00-127.00  105
125  \w    -25.00  80.00   1.00    1.00    --   42.81 -95.00 123.00  105
126  \w    -25.00  80.00   1.00    1.00    --   42.81 -95.00 123.00  105
127  \w     26.00 139.00   1.00    2.00    --  103.32 -15.00  90.00  113
128  \w     67.00 178.00   1.00    2.00    --  103.32  15.00-120.00  111
129  \w     26.00 139.00   1.00    2.00    --  103.32 -15.00  60.00  113
130  \w     67.00 178.00   1.00    2.00    --  103.32  15.00-150.00  111
131  \w     67.00 178.00   1.00    2.00    --  103.32  15.00-180.00  111
132  \w     26.00 139.00   1.00    2.00    --  103.32 -15.00 150.00  113
133  \w     67.00 178.00   1.00    2.00    --  103.32  15.00 -90.00  111
134  \w     67.00 178.00   1.00    2.00    --  103.32  15.00 -60.00  111
135  \w     67.00 178.00   1.00    2.00    --  103.32  15.00 -30.00  111
136  \w     26.00 139.00   1.00    2.00    --  103.32 -15.00 120.00  113
137  \w    -25.00  70.00   1.00    1.00    --   42.81 -95.00 123.00   95
;
_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      0.0438810000
_diffrn_orient_matrix_UB_12      -0.2415039000
_diffrn_orient_matrix_UB_13      0.0097278000
_diffrn_orient_matrix_UB_21      0.0043768000
_diffrn_orient_matrix_UB_22      0.0075667000
_diffrn_orient_matrix_UB_23      0.1204705000
_diffrn_orient_matrix_UB_31      -0.1144110000
_diffrn_orient_matrix_UB_32      -0.0922648000
_diffrn_orient_matrix_UB_33      -0.0155673000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0654
_diffrn_reflns_av_unetI/netI     0.0252
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            36932
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.987
_diffrn_reflns_theta_min         3.496
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    0.696
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.479
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (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    1.330
_exptl_crystal_description       plank
_exptl_crystal_F_000             408
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: petroleum ether, EtOAc'
_exptl_crystal_size_max          0.655
_exptl_crystal_size_mid          0.105
_exptl_crystal_size_min          0.086
_refine_diff_density_max         0.183
_refine_diff_density_min         -0.168
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 1695 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.05(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     264
_refine_ls_number_reflns         3873
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0290
_refine_ls_R_factor_gt           0.0286
_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^)+(0.0440P)^2^+0.1425P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0737
_refine_ls_wR_factor_ref         0.0741
_reflns_Friedel_coverage         0.808
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.984
_reflns_number_gt                3826
_reflns_number_total             3873
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc05246a2.cif
_cod_data_source_block           tlnnlj
_cod_depositor_comments
;Adding full bibliography for 1557079--1557081.cif.

 Adding full bibliography for 1557079--1557081.cif.
;
_cod_original_cell_volume        962.353(17)
_cod_database_code               1557079
_nottingham_internal_coll_name   TLNNLJ
_nottingham_internal_coll_number 17440
_nottingham_internal_coll_client TLNN/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   pczwl
_nottingham_internal_coll_date   15/12/2017
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVA, PL13110002'
_nottingham_internal_process_date 23/01/2018
_nottingham_internal_process_user pczwl
_nottingham_internal_solution_date 21/3/2018
_nottingham_internal_solution_user pczwl
_nottingham_internal_refinement_date 23/3/2018
_nottingham_internal_refinement_user pczwl
_nottingham_internal_validation_date 24/4/2018
_nottingham_internal_validation_user pczwl
_nottingham_internal_archive_date 24/4/2018
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C25 H25 N O3'
_chemical_oxdiff_usercomment
'TLNNLJ #17440 GVA-1357 IN FOMBLIN FILM ON A MICROMOUNT FOR TLNN/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.a Ternary CH refined with riding coordinates:
 C4(H4)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C10(H10), C11(H11), C17(H17), C18(H18), C19(H19), C20(H20),
 C21(H21), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28)
2.d X=CH2 refined with riding coordinates:
 C29(H29A,H29B)
2.e Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C)
2.f Idealised tetrahedral OH refined as rotating group:
 O15(H15)
;
_shelx_res_checksum              24782
_olex2_date_sample_data_collection 2018-01-23
_olex2_date_sample_submission    2017-12-15
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_olex2_submission_original_sample_id NH503
_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 4.708
_oxdiff_exptl_absorpt_empirical_full_min 0.654