SmI2-Mediated Radical Coupling Strategy to Securinega Alkaloids: Total Synthesis of (-)-14,15-Dihydrosecurinine and Formal Total Synthesis of (-)-Securinine.
Zheng, Xiao; Liu, Juan; Ye, Chen-Xi; Wang, Ao; Wang, Ai-E; Huang, Pei-Qiang; The Journal of organic chemistry 80 (2015) 1034–1041; doi:10.1021/jo502522x

data_4030399
_publ_section_title
;
 SmI2-Mediated Radical Coupling Strategy to Securinega Alkaloids: Total
 Synthesis of (-)-14,15-Dihydrosecurinine and Formal Total Synthesis of
 (-)-Securinine.
;
_journal_issue                   2
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              1034
_journal_page_last               1041
_journal_paper_doi               10.1021/jo502522x
_journal_volume                  80
_journal_year                    2015
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C16 H27 Br N2 O3'
_chemical_formula_sum            'C16 H27 Br N2 O3'
_chemical_formula_weight         379.09
_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'
_symmetry_Int_Tables_number      19
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_audit_creation_date             2014-11-02
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.2050(14)
_cell_length_b                   8.1355(18)
_cell_length_c                   35.791(8)
_cell_measurement_reflns_used    5478
_cell_measurement_temperature    273.15
_cell_measurement_theta_max      26.50
_cell_measurement_theta_min      2.28
_cell_volume                     1806.8(7)
_computing_cell_refinement       'SAINT v6.28A (Bruker, 2002)'
_computing_data_reduction        'SAINT v6.28A (Bruker, 2002)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2013)'
_diffrn_ambient_temperature      273.15
_diffrn_measured_fraction_theta_full 0.9947
_diffrn_measured_fraction_theta_max 0.9346
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0381
_diffrn_reflns_av_unetI/netI     0.0462
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       47
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            15503
_diffrn_reflns_theta_full        25.0000
_diffrn_reflns_theta_max         28.60
_diffrn_reflns_theta_min         2.28
_exptl_absorpt_coefficient_mu    2.288
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.765855
_exptl_absorpt_process_details
;
SADABS v.2.03 (Bruker,200?) was used for absorption correction.
R(int) was 0.1434 before and 0.0540 after correction.
The Ratio of minimum to maximum transmission is 0.7659.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_density_diffrn    1.3796
_exptl_crystal_description       pillar
_exptl_crystal_F_000             783.2150
_refine_diff_density_max         0.9193
_refine_diff_density_min         -0.3512
_refine_diff_density_rms         0.0821
_refine_ls_abs_structure_details
'Flack, H. D. (1983). Acta Cryst. A39, 876-881.'
_refine_ls_abs_structure_Flack   0.033(10)
_refine_ls_d_res_high            0.7424
_refine_ls_d_res_low             8.9477
_refine_ls_goodness_of_fit_ref   0.9612
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    41
_refine_ls_number_parameters     202
_refine_ls_number_reflns         4315
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.9612
_refine_ls_R_factor_all          0.0530
_refine_ls_R_factor_gt           0.0388
_refine_ls_shift/su_max          0.0008
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0522P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0894
_refine_ls_wR_factor_ref         0.0945
_reflns_Friedel_coverage         0.897
_reflns_limit_h_max              8
_reflns_limit_h_min              -8
_reflns_limit_k_max              10
_reflns_limit_k_min              -10
_reflns_limit_l_max              47
_reflns_limit_l_min              -46
_reflns_number_gt                3361
_reflns_number_total             4315
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            jo502522x_si_002.cif
_cod_data_source_block           a
_cod_depositor_comments
;
         Adding full bibliography for 4030399.cif.

2020-10-09
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_cell_volume        1806.7(7)
_cod_original_formula_moiety     '0.11(C16 H27 Br N2 O3)'
_cod_original_formula_sum        'C1.778 H3 Br0.111 N0.222 O0.333'
_cod_original_formula_units_Z    36
_cod_original_formula_weight     41.70
_cod_database_code               4030399
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C4(H4), C16(H16), C17(H17)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2a,H2b), C7(H7a,H7b), C8(H8a,H8b), C14(H14a,H14b), C18(H18a,H18b),
 C20(H20a,H20b), C22(H22a,H22b)
2.c Idealised Me refined as rotating group:
 C19(H19a,H19b,H19c), C25(H25a,H25b,H25c), C27(H27a,H27b,H27c)
2.d Idealised tetrahedral OH refined as rotating group:
 O11(H11)
;
_olex2_submission_special_instructions 'No special instructions were received'