Multicomponent domino synthesis of 6-azabicyclo[3.2.1]octanes and their cascade ring expansion toward 2-azabicyclo[4.3.1]decanes.
Natarajan, Nithya; Mouttousadeappane, Dhanavardini; Gnanasambandam, Vasuki; Organic & biomolecular chemistry 24 (2026) 2469–2480; doi:10.1039/d5ob01817j

data_7161100
_publ_section_title
;
 Multicomponent domino synthesis of 6-azabicyclo[3.2.1]octanes and their
 cascade ring expansion toward 2-azabicyclo[4.3.1]decanes.
;
_journal_issue                   12
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2469
_journal_page_last               2480
_journal_paper_doi               10.1039/d5ob01817j
_journal_volume                  24
_journal_year                    2026
_chemical_formula_moiety         'C36 H18 F6 N8 O, C5 H11 N, 2(C3 H7 N O)'
_chemical_formula_sum            'C47 H43 F6 N11 O3'
_chemical_formula_weight         923.92
_chemical_name_systematic        MNBF
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2022-10-12
_audit_creation_method
;
Olex2 1.2-ac21
(compiled 2015.09.16 svn.r134, GUI svn.r4998)
;
_audit_update_record
;
2025-12-28 deposited with the CCDC.	2026-02-19 downloaded from the CCDC.
;
_cell_angle_alpha                117.811(2)
_cell_angle_beta                 105.207(3)
_cell_angle_gamma                99.479(2)
_cell_formula_units_Z            2
_cell_length_a                   13.9052(8)
_cell_length_b                   13.9260(9)
_cell_length_c                   14.7055(13)
_cell_measurement_reflns_used    9654
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      30.413
_cell_measurement_theta_min      2.971
_cell_volume                     2288.9(3)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'four-circle diffractometer'
_diffrn_measurement_method       'Xcalibur, Eos'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0376
_diffrn_reflns_av_unetI/netI     0.0172
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            91057
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        24.998
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         3.028
_diffrn_standards_decay_%        1.2
_diffrn_standards_interval_count 200
_diffrn_standards_number         3
_exptl_absorpt_coefficient_mu    0.104
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.7135
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0838 before and 0.0583 after correction.
The Ratio of minimum to maximum transmission is 0.9563.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'metallic light yellow'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.341
_exptl_crystal_description       block
_exptl_crystal_F_000             960
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.980
_refine_diff_density_min         -0.476
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     677
_refine_ls_number_reflns         8049
_refine_ls_number_restraints     258
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0857
_refine_ls_R_factor_gt           0.0693
_refine_ls_shift/su_max          0.030
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1266P)^2^+2.0091P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1979
_refine_ls_wR_factor_ref         0.2226
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6381
_reflns_number_total             8049
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01817j2.cif
_cod_data_source_block           mnbf
_cod_database_code               7161100
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.980
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N8-H8A = N8-H8B = N7-H7A = N7-H7B
 0.85 with sigma of 0.02
 H8A-H8B = H7A-H7B
 1.38 with sigma of 0.02
 C36-F1 \\sim C36-F2 \\sim C36-F3 \\sim C36-F1' \\sim C36-F2' \\sim C36-F3'
 with sigma of 0.02
 C29-F4 \\sim C29-F5 \\sim C29-F6 \\sim C29-F4' \\sim C29-F5' \\sim C29-F6'
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C36 \\sim F1 \\sim F2 \\sim F3 \\sim F1' \\sim F2' \\sim F3': within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04
C29 \\sim F4 \\sim F5 \\sim F6 \\sim F4' \\sim F5' \\sim F6': within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(F4) \\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(F4') \\sim
Ueq, Uanis(F5') \\sim Ueq, Uanis(F6') \\sim Ueq: with sigma of 0.02 and sigma
for terminal atoms of 0.04
Uanis(F1) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F1') \\sim
Ueq, Uanis(F2') \\sim Ueq, Uanis(F3') \\sim Ueq: with sigma of 0.02 and sigma
for terminal atoms of 0.04
4. Others
 Sof(F1')=Sof(F2')=Sof(F3')=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
 Sof(F4')=Sof(F5')=Sof(F6')=1-FVAR(2)
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C12(H12), C16(H16)
5.b Secondary CH2 refined with riding coordinates:
 C38(H38A,H38B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B), C42(H42A,H42B)
5.c Me refined with riding coordinates:
 C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C47(H47A,H47B,H47C), C48(H48A,H48B,
 H48C)
5.d Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C24(H24), C25(H25), C27(H27), C28(H28),
 C31(H31), C32(H32), C34(H34), C35(H35), C43(H43), C46(H46)
;
_shelx_res_checksum              92488
_shelx_shelxl_version_number     2014/7
_olex2_submission_original_sample_id MNBF
_olex2_submission_special_instructions 'No special instructions were received'