Coupling Catalytic Alkene Hydroacylation and α-Arylation: Enantioselective Synthesis of Heterocyclic Ketones with α-Chiral Quaternary Stereocenters
Ghosh, Avipsa; Walker, James A.; Ellern, Arkady; Stanley, Levi M.; ACS Catalysis 6 (2016) 2673–; doi:10.1021/acscatal.6b00365

data_4513858
_publ_section_title
;
 Coupling Catalytic Alkene Hydroacylation and \a-Arylation:
 Enantioselective Synthesis of Heterocyclic Ketones with \a-Chiral
 Quaternary Stereocenters
;
_journal_issue                   4
_journal_name_full               'ACS Catalysis'
_journal_page_first              2673
_journal_paper_doi               10.1021/acscatal.6b00365
_journal_volume                  6
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H19 N O2'
_chemical_formula_sum            'C20 H19 N O2'
_chemical_formula_weight         305.36
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-04-16
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   7.23695(10)
_cell_length_b                   9.22435(11)
_cell_length_c                   23.1301(3)
_cell_measurement_reflns_used    9022
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.0770
_cell_measurement_theta_min      3.7900
_cell_volume                     1544.08(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.30a (Agilent, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.30a (Agilent, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.30a (Agilent, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3756
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

--------------------------------------------------------------------------
  1  \w   -118.00 -15.00   1.00    1.00    --  -41.65 -37.00  30.00  103
  2  \w   -124.00 -79.00   1.00    1.00    --  -41.65 -99.00  60.00   45
  3  \w    -96.00  -2.00   1.00    1.00    --  -41.65 125.00 -60.00   94
  4  \w   -124.00 -79.00   1.00    1.00    --  -41.65 -99.00-150.00   45
  5  \w     33.00 122.00   1.00    1.00    --  108.29-125.00  30.00   89
  6  \w     24.00 109.00   1.00    1.00    --  108.29 -94.00  90.00   85
  7  \w     94.00 178.00   1.00    1.00    --  108.29 125.00  60.00   84
  8  \w     78.00 178.00   1.00    1.00    --  108.29  30.00 -60.00  100
  9  \w     94.00 178.00   1.00    1.00    --  108.29 125.00   0.00   84
 10  \w     75.00 178.00   1.00    1.00    --  108.29  77.00  60.00  103
 11  \w   -120.00  -8.00   1.00    1.00    --  -41.65 -77.00 -90.00  112
 12  \w   -116.00 -12.00   1.00    1.00    --  -41.65 -57.00 150.00  104
 13  \w      1.00  84.00   1.00    1.00    --   41.65 -99.00 120.00   83
 14  \w     81.00 178.00   1.00    1.00    --  108.29  45.00-120.00   97
 15  \w     75.00 178.00   1.00    1.00    --  108.29  77.00 -30.00  103
 16  \w     78.00 178.00   1.00    1.00    --  108.29  61.00 120.00  100
 17  \w     78.00 145.00   1.00    1.00    --  108.29  61.00  30.00   67
 18  \w     81.00 178.00   1.00    1.00    --  108.29  45.00-180.00   97
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0239928000
_diffrn_orient_matrix_UB_12      0.1212288000
_diffrn_orient_matrix_UB_13      -0.0451878000
_diffrn_orient_matrix_UB_21      -0.0787038000
_diffrn_orient_matrix_UB_22      -0.1110302000
_diffrn_orient_matrix_UB_23      -0.0432505000
_diffrn_orient_matrix_UB_31      -0.1963014000
_diffrn_orient_matrix_UB_32      0.0296730000
_diffrn_orient_matrix_UB_33      0.0228642000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0347
_diffrn_reflns_av_unetI/netI     0.0239
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            14807
_diffrn_reflns_theta_full        72.00
_diffrn_reflns_theta_max         73.95
_diffrn_reflns_theta_min         3.82
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.671
_exptl_absorpt_correction_T_max  0.954
_exptl_absorpt_correction_T_min  0.845
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.30a (Agilent, 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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.314
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             648
_exptl_crystal_size_max          0.491
_exptl_crystal_size_mid          0.128
_exptl_crystal_size_min          0.093
_refine_diff_density_max         0.183
_refine_diff_density_min         -0.182
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.1(2)
_refine_ls_extinction_coef       0.0058(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     211
_refine_ls_number_reflns         3101
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0319
_refine_ls_R_factor_gt           0.0295
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0374P)^2^+0.3180P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0728
_refine_ls_wR_factor_ref         0.0751
_reflns_number_gt                2952
_reflns_number_total             3101
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            cs6b00365_si_002.cif
_cod_data_source_block           ark1a
_cod_depositor_comments          'Adding full bibliography for 4513858.cif.'
_cod_original_cell_volume        1544.07(3)
_cod_database_code               4513858
_chemical_oxdiff_formula         'C20 H19 N O2'
_reflns_odcompleteness_completeness 99.88
_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.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C7(H7), C15(H15), C17(H17), C18(H18), C19(H19)
2.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C20(H20A,H20B,H20C)
;
_olex2_date_sample_data_collection 2015-04-15
_olex2_date_sample_submission    2015-04-01
_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 1.321
_oxdiff_exptl_absorpt_empirical_full_min 0.537