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_1557081
_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_compound_source        'petroleum ether, EtOAc'
_chemical_formula_moiety         'C25 H25 N O3 S'
_chemical_formula_sum            'C25 H25 N O3 S'
_chemical_formula_weight         419.52
_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
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-07-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-08-07 deposited with the CCDC.	2020-01-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.90900(10)
_cell_length_b                   12.8175(2)
_cell_length_c                   27.4929(4)
_cell_measurement_reflns_used    6654
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      72.6990
_cell_measurement_theta_min      4.7020
_cell_volume                     2082.27(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_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    'ShelXT (Sheldrick, 2015)'
_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 0.988
_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    5.00    --  -41.70  19.00 150.00   43
  2  \w   -114.00 -14.00   1.00    5.00    --  -41.70 -57.00-150.00  100
  3  \w     -5.00  38.00   1.00    5.00    --  -41.70  19.00-150.00   43
  4  \w     -5.00  38.00   1.00    5.00    --  -41.70  19.00-180.00   43
  5  \w     32.00  93.00   1.00   20.00    --  104.36 -61.00  60.00   61
  6  \w     31.00 112.00   1.00   20.00    --  104.36-125.00-120.00   81
  7  \w     28.00  57.00   1.00   20.00    --  104.36 -30.00  30.00   29
  8  \w     31.00  72.00   1.00   20.00    --  104.36 -45.00 -90.00   41
  9  \w     28.00  57.00   1.00   20.00    --  104.36 -30.00 -60.00   29
 10  \w     76.00 178.00   1.00   20.00    --  104.36  30.00-180.00  102
 11  \w     97.00 177.00   1.00   20.00    --  104.36 126.00 -88.00   80
 12  \w     28.00  57.00   1.00   20.00    --  104.36 -30.00   0.00   29
 13  \w     31.00 104.00   1.00   20.00    --  104.36-125.00  60.00   73
;
_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      -0.0700018000
_diffrn_orient_matrix_UB_12      0.0912566000
_diffrn_orient_matrix_UB_13      0.0332129000
_diffrn_orient_matrix_UB_21      0.0320028000
_diffrn_orient_matrix_UB_22      -0.0700756000
_diffrn_orient_matrix_UB_23      0.0450089000
_diffrn_orient_matrix_UB_31      0.2490624000
_diffrn_orient_matrix_UB_32      0.0346879000
_diffrn_orient_matrix_UB_33      0.0035567000
_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  0.0175
_diffrn_reflns_av_unetI/netI     0.0214
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            9854
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.811
_diffrn_reflns_theta_min         3.805
_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    1.598
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.521
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.45a (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    1.338
_exptl_crystal_description       needle
_exptl_crystal_F_000             888
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.872
_exptl_crystal_size_mid          0.072
_exptl_crystal_size_min          0.049
_refine_diff_density_max         0.189
_refine_diff_density_min         -0.241
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 1615 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.008(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     276
_refine_ls_number_reflns         4075
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0243
_refine_ls_R_factor_gt           0.0234
_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^)+(0.0286P)^2^+0.4043P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0577
_refine_ls_wR_factor_ref         0.0583
_reflns_Friedel_coverage         0.698
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.960
_reflns_number_gt                3979
_reflns_number_total             4075
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc05246a2.cif
_cod_data_source_block           rshlog
_cod_depositor_comments
;Adding full bibliography for 1557079--1557081.cif.

 Adding full bibliography for 1557079--1557081.cif.
;
_cod_database_code               1557081
_nottingham_internal_coll_name   RSHLOG
_nottingham_internal_coll_number 18292
_nottingham_internal_coll_client RDS/HWL
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '20.00, 5.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pczspa
_nottingham_internal_coll_date   17/07/2019
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVB, PL13110001'
_nottingham_internal_process_date 18/07/2019
_nottingham_internal_process_user pczspa
_nottingham_internal_solution_date 28/07/2019
_nottingham_internal_solution_user pczspa
_nottingham_internal_refinement_date 28/07/2019
_nottingham_internal_refinement_user pczspa
_nottingham_internal_validation_date 28/07/2019
_nottingham_internal_validation_user pczspa
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         C25H25NO3S
_chemical_oxdiff_usercomment
'GVB-1650 RSHLOG #18292 for RDS/HWL in fomblin film on a micromount'
_shelx_estimated_absorpt_t_max   0.926
_shelx_estimated_absorpt_t_min   0.336
_reflns_odcompleteness_completeness 99.91
_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
 O6-H6
 0.84 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C4(H4)
3.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C5(H5A,H5B)
3.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C16(H16), C17(H17), C18(H18),
 C19(H19), C20(H20), C25(H25), C26(H26), C28(H28), C29(H29)
3.d X=CH2 refined with riding coordinates:
 C14(H14A,H14B)
3.e Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C)
;
_shelx_res_checksum              83653
_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 1.179
_oxdiff_exptl_absorpt_empirical_full_min 0.868