Light-Mediated Chiral Phosphate Catalysis for Asymmetric Dicarbofunctionalization of Enamides
Shen, Yang; Shen, Meng-Lan; Wang, Pu-Sheng; ACS Catalysis  (2020) 8247–8253; doi:10.1021/acscatal.0c02660

data_4517851
_publ_section_title
;
 Light-Mediated Chiral Phosphate Catalysis for Asymmetric
 Dicarbofunctionalization of Enamides
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              8247
_journal_page_last               8253
_journal_paper_doi               10.1021/acscatal.0c02660
_journal_year                    2020
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C25 H23 F N2 O'
_chemical_formula_sum            'C25 H23 F N2 O'
_chemical_formula_weight         386.45
_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     dual
_audit_creation_date             2019-12-13
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.2261(3)
_cell_length_b                   9.7377(4)
_cell_length_c                   22.6198(9)
_cell_measurement_reflns_used    4614
_cell_measurement_temperature    170(2)
_cell_measurement_theta_max      54.88
_cell_measurement_theta_min      3.40
_cell_volume                     2032.19(13)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      169.98
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0573
_diffrn_reflns_av_unetI/netI     0.0428
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            16853
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         54.884
_diffrn_reflns_theta_min         4.300
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.431
_exptl_absorpt_correction_T_max  0.7508
_exptl_absorpt_correction_T_min  0.4576
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1635 before and 0.0839 after correction. The Ratio of minimum to maximum transmission is 0.5360. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.263
_exptl_crystal_description       block
_exptl_crystal_F_000             816
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.227
_refine_diff_density_min         -0.203
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 1437 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.18(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     263
_refine_ls_number_reflns         3859
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0427
_refine_ls_R_factor_gt           0.0386
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0421P)^2^+0.4765P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0925
_refine_ls_wR_factor_ref         0.0960
_reflns_Friedel_coverage         0.735
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.993
_reflns_number_gt                3607
_reflns_number_total             3859
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c02660_si_001.cif
_cod_data_source_block           191213sy_0m
_cod_depositor_comments          'Adding full bibliography for 4517851.cif.'
_cod_database_code               4517851
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.979
_shelx_estimated_absorpt_t_min   0.966
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2), C3(H3), C6(H6), C7(H7), C8(H8), C9(H9), C13(H13), C14(H14),
 C15(H15), C16(H16), C17(H17), C21(H21), C23(H23), C24(H24), C25(H25)
2.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C)
;
_shelx_res_checksum              68072
_shelx_hkl_checksum              1794
_olex2_submission_special_instructions 'No special instructions were received'