Direct photochemical intramolecular [4 + 2] cycloadditions of dehydrosecodine-type substrates for the synthesis of the <i>iboga</i>-type scaffold and divergent [2 + 2] cycloadditions employing micro-flow system.
Tay, Gavin; Nishimura, Soushi; Oguri, Hiroki; Chemical science 15 (2024) 15599–15609; doi:10.1039/d4sc02597k

data_1572691
_publ_section_title
;
 Direct photochemical intramolecular [4 + 2] cycloadditions of
 dehydrosecodine-type substrates for the synthesis of the
 <i>iboga</i>-type scaffold and divergent [2 + 2] cycloadditions employing
 micro-flow system.
;
_journal_issue                   38
_journal_name_full               'Chemical science'
_journal_page_first              15599
_journal_page_last               15609
_journal_paper_doi               10.1039/d4sc02597k
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C27 H34 N2 O5 Si'
_chemical_formula_sum            'C27 H34 N2 O5 Si'
_chemical_formula_weight         494.65
_chemical_name_systematic        1202_GT_iboga_Wayama
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-10-05
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2024-02-19 deposited with the CCDC.	2024-08-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 117.635(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.073(6)
_cell_length_b                   6.658(2)
_cell_length_c                   21.467(6)
_cell_measurement_reflns_used    4522
_cell_measurement_temperature    300.00
_cell_measurement_theta_max      0.1575
_cell_measurement_theta_min      0.0263
_cell_volume                     2668.3(13)
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      300.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker Venture D8'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1940
_diffrn_reflns_av_unetI/netI     0.2084
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            24702
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.143
_diffrn_reflns_theta_min         1.849
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.126
_exptl_absorpt_correction_T_max  0.84794
_exptl_absorpt_correction_T_min  0.97330
_exptl_absorpt_process_details   none
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.231
_exptl_crystal_description       block
_exptl_crystal_F_000             1056
_exptl_crystal_preparation       'Vapordiffusion using CHCl2/n-hexane'
_exptl_crystal_recrystallization_method 'Vapordiffusion using CHCl2/n-hexane'
_exptl_crystal_size_max          0.509
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.048
_refine_diff_density_max         0.233
_refine_diff_density_min         -0.325
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.893
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     321
_refine_ls_number_reflns         5304
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.893
_refine_ls_R_factor_all          0.2993
_refine_ls_R_factor_gt           0.0879
_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^)+(0.1420P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2275
_refine_ls_wR_factor_ref         0.3378
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1260
_reflns_number_total             5304
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02597k2.cif
_cod_data_source_block           mo_1202_gt_iboga_0m_a
_cod_depositor_comments
'Adding full bibliography for 1572691--1572693.cif.'
_cod_original_cell_volume        2668.5(14)
_cod_database_code               1572691
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.994
_shelx_estimated_absorpt_t_min   0.938
_exptl_absorpt_special_details   none
_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.a Ternary CH refined with riding coordinates:
 C00C(H00C), C00I(H00I)
2.b Secondary CH2 refined with riding coordinates:
 C00K(H00A,H00B), C00L(H00D,H00E), C00N(H00F,H00G), C00P(H00H,H00J), C00R(H00P,
 H00Q), C00V(H00R,H00V)
2.c Aromatic/amide H refined with riding coordinates:
 C00M(H00M), C00O(H00O), C00S(H00S), C00T(H00T), C00U(H00U)
2.d Idealised Me refined as rotating group:
 C00Q(H00K,H00L,H00N), C00W(H00W,H00X,H00Y), C00X(H00Z,H,HA), C00Y(H00,HB,HC),
 C00Z(H1,HD,HE)
;
_shelx_res_checksum              39722
_olex2_exptl_crystal_mounting_method 'Manual mounting by using Rigaku-loop'
_olex2_submission_original_sample_id 1202_GT_iboga_Wayama
_olex2_submission_special_instructions 'No special instructions were received'