Transition Metal Catalyzed Stereodivergent Synthesis of syn- and anti-δ-Vinyl-Lactams: Formal Total Synthesis of (−)-Cermizine C and (−)-Senepodine G
Breit, Bernhard; Schmidt, Johannes; Chemical Science  (2019) –; doi:10.1039/C8SC05502E

data_1550526
_publ_section_title
;
 Transition Metal Catalyzed Stereodivergent Synthesis of syn- and
 anti-\d-Vinyl-Lactams: Formal Total Synthesis of (&#x2212;)-Cermizine C
 and (&#x2212;)-Senepodine G
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C8SC05502E
_journal_year                    2019
_chemical_formula_moiety         'C20 H21 N O3 S'
_chemical_formula_sum            'C20 H21 N O3 S'
_chemical_formula_weight         355.44
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.18 svn.r3508 for OlexSys, GUI svn.r5497)
;
_audit_update_record
;
2018-05-25 deposited with the CCDC.
2019-01-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.20(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.136(8)
_cell_length_b                   17.429(15)
_cell_length_c                   13.045(14)
_cell_measurement_reflns_used    9898
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.825
_cell_measurement_theta_min      2.860
_cell_volume                     1785(3)
_computing_cell_refinement       'SAINT V8.38A (Madison, 2016)'
_computing_data_collection       'Bruker APEX2 software'
_computing_data_reduction        'SAINT V8.38A (Madison, 2016)'
_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      100.01
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_device       'fixed-chi two circle goniometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0302
_diffrn_reflns_av_unetI/netI     0.0226
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            20123
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.643
_diffrn_reflns_theta_min         1.996
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           50
_diffrn_source_type              'Incoatec Mo I\ms'
_diffrn_source_voltage           0.6
_exptl_absorpt_coefficient_mu    0.200
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.6962
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1108 before and 0.0416 after correction. The Ratio of minimum to maximum transmission is 0.9335. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.323
_exptl_crystal_description       block
_exptl_crystal_F_000             752
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.376
_refine_diff_density_min         -0.361
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     311
_refine_ls_number_reflns         4497
_refine_ls_number_restraints     529
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0383
_refine_ls_R_factor_gt           0.0349
_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^)+(0.0362P)^2^+0.9017P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0863
_refine_ls_wR_factor_ref         0.0884
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4117
_reflns_number_total             4497
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc05502e2.cif
_cod_data_source_block           breitjs_6_53_0m_a
_cod_database_code               1550526
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.957
_shelx_estimated_absorpt_t_min   0.942
_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. Restrained distances
 C8-C9 \\sim C8A-C9A
 with sigma of 0.02
 C8-C13 \\sim C8A-C13A
 with sigma of 0.02
 C9-C10 \\sim C9A-C10A
 with sigma of 0.02
 C10-C11 \\sim C10A-C11A
 with sigma of 0.02
 C11-C12 \\sim C11A-C12A
 with sigma of 0.02
 C12-C13 \\sim C12A-C13A
 with sigma of 0.02
 C6-C8 \\sim C6-C8A
 with sigma of 0.04
 C8-C10 \\sim C8A-C10A
 with sigma of 0.04
 C8-C12 \\sim C8A-C12A
 with sigma of 0.04
 C9-C11 \\sim C9A-C11A
 with sigma of 0.04
 C9-C13 \\sim C9A-C13A
 with sigma of 0.04
 C10-C12 \\sim C10A-C12A
 with sigma of 0.04
 C11-C13 \\sim C11A-C13A
 with sigma of 0.04
 C6-C7 \\sim C6A-C7
 with sigma of 0.02
 C6-C5A \\sim C6A-C5A
 with sigma of 0.02
 C4-C8 \\sim C4-C8A
 with sigma of 0.04
 C4-C5A \\sim C4A-C5A
 with sigma of 0.02
 C1-C4 \\sim C1-C4A
 with sigma of 0.02
 C5-C6 \\sim C5A-C6
 with sigma of 0.02
 C5-C8 \\sim C5A-C8A
 with sigma of 0.02
 C5-C9 \\sim C5A-C9A
 with sigma of 0.04
 C5-C13 \\sim C5A-C13A
 with sigma of 0.04
 C5-C6 \\sim C5-C6A
 with sigma of 0.02
 C4-C5 \\sim C4-C5A
 with sigma of 0.02
 C4-C5 \\sim C4A-C5
 with sigma of 0.02
 C6-C5 \\sim C6A-C5A
 with sigma of 0.02
 C7-C6A \\sim C7-C6
 with sigma of 0.02
 C5A-C4A \\sim C5-C4
 with sigma of 0.02
 C4-C1 \\sim C4A-C1
 with sigma of 0.02
3. Restrained planarity
 C8A, C13A, C12A, C11A, C10A, C9A
 with sigma of 0.06
 C8, C13, C12, C11, C10, C9
 with sigma of 0.06
4. Rigid bond restraints
 C4, C5, C6, C8, C9, C10, C11, C12, C13, C5A, C8A, C9A, C10A, C11A, C12A, C13A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C4 \\sim H4A \\sim H4B \\sim C5 \\sim H5 \\sim C6 \\sim H6A \\sim H6B \\sim C8
\\sim C9 \\sim H9 \\sim C10 \\sim H10 \\sim C11 \\sim H11 \\sim C12 \\sim H12
\\sim C13 \\sim H13 \\sim C5A \\sim H5A \\sim C8A \\sim C9A \\sim H9A \\sim
C10A \\sim H10A \\sim C11A \\sim H11A \\sim C12A \\sim H12A \\sim C13A \\sim
H13A \\sim C4A \\sim H4AA \\sim H4AB \\sim C6A \\sim H6AA \\sim H6AB: within
1.1A with sigma of 0.01 and sigma for terminal atoms of 0.02
C4 \\sim C5 \\sim C6 \\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13
\\sim C5A \\sim C8A \\sim C9A \\sim C10A \\sim C11A \\sim C12A \\sim C13A \\sim
C4A \\sim C6A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
6. Others
 Sof(C5A)=Sof(H5A)=Sof(C8A)=Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(H10A)=Sof(C11A)=
 Sof(H11A)=Sof(C12A)=Sof(H12A)=Sof(C13A)=Sof(H13A)=1-FVAR(1)
 Sof(C5)=Sof(H5)=Sof(C8)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10)=Sof(C11)=Sof(H11)=
 Sof(C12)=Sof(H12)=Sof(C13)=Sof(H13)=FVAR(1)
 Sof(H1B)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=1-FVAR(2)
 Sof(H1A)=Sof(C4)=Sof(H4A)=Sof(H4B)=FVAR(2)
 Sof(C6A)=Sof(H6AA)=Sof(H6AB)=1-FVAR(3)
 Sof(C6)=Sof(H6A)=Sof(H6B)=FVAR(3)
7.a Ternary CH refined with riding coordinates:
 C1(H1A), C1(H1B), C5(H5), C5A(H5A)
7.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C6(H6A,H6B), C4A(H4AA,H4AB), C6A(H6AA,H6AB)
7.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C15(H15), C16(H16),
 C18(H18), C19(H19), C9A(H9A), C10A(H10A), C11A(H11A), C12A(H12A), C13A(H13A)
7.d X=CH2 refined with riding coordinates:
 C3(H3A,H3B)
7.e Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C)
;
_shelx_res_checksum              35595
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems 800'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_special_instructions 'No special instructions were received'