Total synthesis of (±)-3-demethoxyerythratidinone <i>via</i> Tf<sub>2</sub>O-promoted cascade reaction of enaminone.
Lou, Mingliang; Liu, Xiaolei; Han, Shoule; Bai, Songlin; Qi, Xiangbing; Chemical communications (Cambridge, England) 60 (2024) 3842–3845; doi:10.1039/d3cc06270h

data_7132833
_publ_section_title
;
 Total synthesis of (&#xb1;)-3-demethoxyerythratidinone <i>via</i>
 Tf<sub>2</sub>O-promoted cascade reaction of enaminone.
;
_journal_issue                   28
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              3842
_journal_page_last               3845
_journal_paper_doi               10.1039/d3cc06270h
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C18 H17 F3 N2 O4 S'
_chemical_formula_sum            'C18 H17 F3 N2 O4 S'
_chemical_formula_weight         414.39
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc26908t
_audit_creation_date             2020-07-12
_audit_creation_method
;
Olex2 1.3
(compiled 2020.06.28 svn.raecde09e for OlexSys, GUI svn.r6132)
;
_audit_update_record
;
2020-09-29 deposited with the CCDC.	2024-03-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   19.42100(10)
_cell_length_b                   13.80990(10)
_cell_length_c                   27.8614(2)
_cell_measurement_reflns_used    25757
_cell_measurement_temperature    99.9(4)
_cell_measurement_theta_max      74.7770
_cell_measurement_theta_min      3.1550
_cell_volume                     7472.49(9)
_computing_cell_refinement       'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.969
_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    -12.00  72.00   0.50    0.07    --    0.00  59.00-160.00  168
  2  \w   -112.00 -28.00   0.50    0.26    --  -99.75  59.00-160.00  168
  3  \w   -170.00 -87.00   0.50    0.26    --  -99.75 -59.00  58.00  166
  4  \w   -170.00 -70.00   0.50    0.26    --  -99.75-130.00-175.00  200
  5  \w    -71.00   6.00   0.50    0.07    --    0.00 -38.00  90.00  154
  6  \w     25.00 103.00   0.50    0.26    --   97.75 -30.00-180.00  156
  7  \w     49.00 104.00   0.50    0.26    --   97.75   0.00  60.00  110
  8  \w     26.00 102.00   0.50    0.26    --   97.75 -15.00-180.00  152
  9  \w    -48.00 -23.00   0.50    0.07    --    0.00   0.00  90.00   50
 10  \w     -6.00  71.00   0.50    0.07    --    0.00  38.00 -90.00  154
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0598898000
_diffrn_orient_matrix_UB_12      -0.0489250000
_diffrn_orient_matrix_UB_13      -0.0269630000
_diffrn_orient_matrix_UB_21      0.0519232000
_diffrn_orient_matrix_UB_22      0.0604827000
_diffrn_orient_matrix_UB_23      0.0291275000
_diffrn_orient_matrix_UB_31      0.0026713000
_diffrn_orient_matrix_UB_32      -0.0799513000
_diffrn_orient_matrix_UB_33      0.0385136000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0277
_diffrn_reflns_av_unetI/netI     0.0209
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            37509
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.917
_diffrn_reflns_theta_min         3.172
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.067
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60504
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.45g (Rigaku Oxford Diffraction, 2018)
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    1.473
_exptl_crystal_description       block
_exptl_crystal_F_000             3424
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.726
_refine_diff_density_min         -0.673
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     519
_refine_ls_number_reflns         7447
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0559
_refine_ls_R_factor_gt           0.0518
_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^)+(0.0567P)^2^+8.4745P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1294
_refine_ls_wR_factor_ref         0.1334
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6840
_reflns_number_total             7447
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc06270h2.cif
_cod_data_source_block           qxb_100k_compound2_a
_cod_depositor_comments
'Adding full bibliography for 7132832--7132833.cif.'
_cod_original_cell_volume        7472.48(9)
_cod_database_code               7132833
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.820
_shelx_estimated_absorpt_t_min   0.789
_reflns_odcompleteness_completeness 99.97
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C33-C32 \\sim C33-C34
 with sigma of 0.02
 C31-C32 \\sim C31-C34
 with sigma of 0.02
3. Others
 Sof(H33C)=Sof(H33D)=Sof(H31C)=Sof(H31D)=Sof(C34)=Sof(H34A)=Sof(H34B)=1-FVAR(1)
 Sof(H33A)=Sof(H33B)=Sof(H31A)=Sof(H31B)=Sof(C32)=Sof(H32A)=Sof(H32B)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C14(H14A,H14B), C13(H13A,H13B), C33(H33A,H33B), C33(H33C,
 H33D), C31(H31A,H31B), C31(H31C,H31D), C32(H32A,H32B), C34(H34A,H34B)
4.b Aromatic/amide H refined with riding coordinates:
 C11(H11), C29(H29), C9(H9), C23(H23), C6(H6), C7(H7), C8(H8), C26(H26),
 C24(H24), C25(H25)
4.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C16(H16A,H16B,
 H16C)
;
_shelx_res_checksum              85278
_shelx_hkl_checksum              97187
_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 2.193
_oxdiff_exptl_absorpt_empirical_full_min 0.624