Highly Enantioselective Synthesis of Functionalized Glutarimide Using Oxidative N-Heterocyclic Carbene Catalysis: A Formal Synthesis of (-)-Paroxetine.
Porey, Arka; Santra, Surojit; Guin, Joyram; The Journal of organic chemistry 84 (2019) 5313–5327; doi:10.1021/acs.joc.9b00320

data_4034339
_publ_section_title
;
 Highly Enantioselective Synthesis of Functionalized Glutarimide Using
 Oxidative N-Heterocyclic Carbene Catalysis: A Formal Synthesis of
 (-)-Paroxetine.
;
_journal_issue                   9
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              5313
_journal_page_last               5327
_journal_paper_doi               10.1021/acs.joc.9b00320
_journal_volume                  84
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C26 H23 I N2 O3'
_chemical_formula_sum            'C26 H23 I N2 O3'
_chemical_formula_weight         538.36
_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
_audit_creation_date             2018-11-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.769(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.6020(6)
_cell_length_b                   18.4031(18)
_cell_length_c                   24.676(3)
_cell_measurement_reflns_used    8664
_cell_measurement_temperature    102(2)
_cell_measurement_theta_max      25.20
_cell_measurement_theta_min      2.48
_cell_volume                     2543.7(5)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      102.19
_diffrn_measured_fraction_theta_full 0.974
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0957
_diffrn_reflns_av_unetI/netI     0.0944
_diffrn_reflns_Laue_measured_fraction_full 0.974
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            26565
_diffrn_reflns_point_group_measured_fraction_full 0.925
_diffrn_reflns_point_group_measured_fraction_max 0.948
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         24.996
_diffrn_reflns_theta_min         2.362
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.286
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.406
_exptl_crystal_description       needle
_exptl_crystal_F_000             1080
_refine_diff_density_max         1.296
_refine_diff_density_min         -1.102
_refine_diff_density_rms         0.122
_refine_ls_abs_structure_details
;
 Flack x determined using 2438 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.08(2)
_refine_ls_extinction_coef       0.0040(13)
_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   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     532
_refine_ls_number_reflns         8515
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.1028
_refine_ls_R_factor_gt           0.0794
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0973P)^2^+11.5065P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1975
_refine_ls_wR_factor_ref         0.2224
_reflns_Friedel_coverage         0.836
_reflns_Friedel_fraction_full    0.871
_reflns_Friedel_fraction_max     0.894
_reflns_number_gt                6646
_reflns_number_total             8515
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00320_si_002.cif
_cod_data_source_block           test9
_cod_database_code               4034339
_shelxl_version_number           2014-3
_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. Uiso/Uaniso restraints and constraints
Uanis(C47) = Uanis(C18)
Uanis(N6) = Uanis(N2)
Uanis(O7) = Uanis(O2)
Uanis(C109) = Uanis(C97)
Uanis(C106) = Uanis(C103)
Uanis(C106) = Uanis(C107)
Uanis(C107) = Uanis(C108)
Uanis(C44) = Uanis(C66)
Uanis(C66) = Uanis(C65)
Uanis(C3) = Uanis(C2)
3. Others
 Sof(I2B)=1-FVAR(1)
 Sof(I2A)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C42(H42), C10(H10), C32(H32), C37(H37)
4.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C33(H33A,H33B)
4.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C2(H2), C16(H16), C11(H11), C15(H15), C13(H13), C23(H23),
 C101(H101), C24(H24), C22(H22), N2(H2A), C27(H27), C31(H31), C30(H30),
 C28(H28), C39(H39), C43(H43), C44(H44), N6(H6), C65(H65), C66(H66), C103(H103),
  C108(H108), C107(H107), C109(H109)
4.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C25(H25A,H25B,H25C), C67(H67A,H67B,H67C), C110(H11A,H11B,
 H11C)
;
_shelx_res_checksum              84492
_shelx_hkl_checksum              7569
_shelx_fab_checksum              44183
_olex2_submission_special_instructions 'No special instructions were received'