Lewis Acid/Brønsted Base-Assisted Palladium Catalysis: Stereoselective Construction of Skeletally Diverse Spiro-Ketolactams from Vinylethylene Carbonates
Huang, Qian-Wei; Qi, Ting; Liu, Yue; Zhang, Xiang; Li, Qing-Zhu; Gou, Chuan; Tao, Ying-Mao; Leng, Hai-Jun; Li, Jun-Long; ACS Catalysis  (2021) 10148–10158; doi:10.1021/acscatal.1c01724

data_4518924
_publ_section_title
;
 Lewis Acid/Br\/onsted Base-Assisted Palladium Catalysis: Stereoselective
 Construction of Skeletally Diverse Spiro-Ketolactams from Vinylethylene
 Carbonates
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              10148
_journal_page_last               10158
_journal_paper_doi               10.1021/acscatal.1c01724
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C28 H25 N O3'
_chemical_formula_sum            'C28 H25 N O3'
_chemical_formula_weight         423.49
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-04-30
_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                90
_cell_formula_units_Z            8
_cell_length_a                   25.0296(3)
_cell_length_b                   21.4254(3)
_cell_length_c                   8.35199(14)
_cell_measurement_reflns_used    8820
_cell_measurement_temperature    295.0(4)
_cell_measurement_theta_max      71.5590
_cell_measurement_theta_min      4.0760
_cell_volume                     4478.91(11)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_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      air
_diffrn_ambient_temperature      295.0(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.991
_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    -53.00  31.00   1.00    1.11    --  -36.29  57.00  60.00   84
  2  \w    -55.00  33.00   1.00    1.11    --  -36.29  38.00-120.00   88
  3  \w     20.00 104.00   1.00    1.11    --   36.29  57.00  30.00   84
  4  \w     23.00  90.00   1.00    1.11    --   36.29-125.00-120.00   67
  5  \w      1.00  75.00   1.00    1.11    --   36.29 -99.00 120.00   74
  6  \w    100.00 176.00   1.00    4.46    --  106.21 111.00 120.00   76
  7  \w    100.00 176.00   1.00    4.46    --  106.21 111.00   0.00   76
  8  \w     57.00 150.00   1.00    4.46    --  106.21 178.00  60.00   93
  9  \w     88.00 173.00   1.00    4.46    --  106.21  61.00 -60.00   85
 10  \w     79.00 174.00   1.00    4.46    --  106.21  77.00-150.00   95
 11  \w     37.00 109.00   1.00    4.46    --  106.21 -94.00-180.00   72
 12  \w     38.00 124.00   1.00    4.46    --  106.21 -45.00 -60.00   86
 13  \w     68.00 177.00   1.00    4.46    --  106.21  15.00 -90.00  109
 14  \w     19.00  74.00   1.00    1.11    --   36.29  49.00 130.00   55
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0201197000
_diffrn_orient_matrix_UB_12      0.0678735000
_diffrn_orient_matrix_UB_13      -0.0097129000
_diffrn_orient_matrix_UB_21      0.0308326000
_diffrn_orient_matrix_UB_22      -0.0157414000
_diffrn_orient_matrix_UB_23      -0.1543841000
_diffrn_orient_matrix_UB_31      -0.0493400000
_diffrn_orient_matrix_UB_32      0.0178197000
_diffrn_orient_matrix_UB_33      -0.1003386000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0406
_diffrn_reflns_av_unetI/netI     0.0346
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            24414
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.714
_diffrn_reflns_theta_min         4.091
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.646
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.52998
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.256
_exptl_crystal_description       block
_exptl_crystal_F_000             1792
_exptl_crystal_size_max          0.75
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.173
_refine_diff_density_min         -0.249
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Flack x determined using 2968 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.04(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     587
_refine_ls_number_reflns         8614
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0556
_refine_ls_R_factor_gt           0.0507
_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^)+(0.0827P)^2^+0.2357P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1324
_refine_ls_wR_factor_ref         0.1390
_reflns_Friedel_coverage         0.764
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.968
_reflns_number_gt                7760
_reflns_number_total             8614
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c01724_si_002.cif
_cod_data_source_block           ljl-hqw-0425
_cod_original_cell_volume        4478.90(12)
_cod_database_code               4518924
_reflns_odcompleteness_completeness 99.85
_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
2. Others
 Sof(H01G)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=1-FVAR(1)
 Sof(H01F)=Sof(C1)=Sof(H1A)=Sof(H1B)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C00K(H00K), C014(H014)
3.b Secondary CH2 refined with riding coordinates:
 C00B(H00C,H00D), C00H(H00A,H00B), C00P(H00E,H00F), C00T(H00G,H00H), C011(H01A,
 H01B), C01A(H01C,H01D)
3.c Aromatic/amide H refined with riding coordinates:
 C00N(H00N), C00Q(H00Q), C00R(H00R), C00S(H00S), C00W(H00W), C00X(H00X),
 C00Y(H00Y), C00Z(H00Z), C010(H010), C012(H012), C013(H013), C015(H015),
 C017(H017), C018(H018), C019(H019), C01B(H01Q), C01C(H01E), C01D(H01F),
 C01D(H01G), C01E(H01H), C01F(H01R), C01G(H01I), C01H(H01J), C01I(H01K),
 C01J(H01L), C01K(H01S), C01L(H01M), C01M(H01T), C01N(H01U), C01O(H01O),
 C01P(H01V), C01Q(H01W), C01R(H01X)
3.d X=CH2 refined with riding coordinates:
 C016(H01N,H01P), C1(H1A,H1B), C1A(H1AA,H1AB)
;
_shelx_res_checksum              31687
_shelx_hkl_checksum              90119
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2019-04-29
_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 1.474
_oxdiff_exptl_absorpt_empirical_full_min 0.702