Transition-metal free, radical oxidation of 1,6-enyne cyclopropanation: synthesis of aza-bicyclo[4.1.0]heptane derivatives.
Meena, Shivam A.; Thakur, Deepika; Nandy, Abhijit; Ranjan, Rahul; Rai, Anubhav; Banerjee, Shibdas; Verma, Akhilesh K.; Chemical communications (Cambridge, England) 60 (2024) 9230–9233; doi:10.1039/d4cc02639j

data_7133438
_publ_section_title
;
 Transition-metal free, radical oxidation of 1,6-enyne cyclopropanation:
 synthesis of aza-bicyclo[4.1.0]heptane derivatives.
;
_journal_issue                   69
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              9230
_journal_page_last               9233
_journal_paper_doi               10.1039/d4cc02639j
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C18 H15 N O3'
_chemical_formula_sum            'C18 H15 N O3'
_chemical_formula_weight         293.31
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-02-04
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-02-04 deposited with the CCDC.	2024-07-31 downloaded from the CCDC.
;
_cell_angle_alpha                103.773(4)
_cell_angle_beta                 97.032(3)
_cell_angle_gamma                114.529(4)
_cell_formula_units_Z            4
_cell_length_a                   10.6199(4)
_cell_length_b                   10.8504(5)
_cell_length_c                   15.1555(6)
_cell_measurement_reflns_used    7219
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      26.8660
_cell_measurement_theta_min      3.5090
_cell_volume                     1493.92(13)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/4 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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      3.00  69.00   0.50    5.00    --    5.23  73.00  85.00  132
  2  \w    -64.00  25.00   0.50    5.00    --    5.23 -73.00 -43.00  178
  3  \w    -16.00  10.00   0.50    5.00    --   -4.91 -99.00 -60.00   52
  4  \w    -22.00  27.00   0.50    5.00    --   -4.91 -99.00 150.00   98
  5  \w    -23.00  28.00   0.50    5.00    --   -4.91 -99.00  30.00  102
  6  \w    -48.00  10.00   0.50    5.00    --    5.23 -57.00  30.00  116
  7  \w     12.00  38.00   0.50    5.00    --    5.23 -99.00-120.00   52
  8  \w     -1.00  47.00   0.50    5.00    --    5.23  38.00-120.00   96
  9  \w    -22.00   3.00   0.50    5.00    --    5.23 -99.00-120.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0322609000
_diffrn_orient_matrix_UB_12      -0.0131420000
_diffrn_orient_matrix_UB_13      0.0373303000
_diffrn_orient_matrix_UB_21      0.0094341000
_diffrn_orient_matrix_UB_22      0.0711006000
_diffrn_orient_matrix_UB_23      0.0143476000
_diffrn_orient_matrix_UB_31      -0.0679747000
_diffrn_orient_matrix_UB_32      -0.0228916000
_diffrn_orient_matrix_UB_33      -0.0296296000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0447
_diffrn_reflns_av_unetI/netI     0.0486
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            21311
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         3.130
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.089
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88031
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.304
_exptl_crystal_description       block
_exptl_crystal_F_000             616
_refine_diff_density_max         0.572
_refine_diff_density_min         -0.277
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     383
_refine_ls_number_reflns         6120
_refine_ls_number_restraints     28
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.1049
_refine_ls_R_factor_gt           0.0652
_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^)+(0.1019P)^2^+0.2925P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1858
_refine_ls_wR_factor_ref         0.2094
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3685
_reflns_number_total             6120
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc02639j2.cif
_cod_data_source_block           smt-317_auto
_cod_depositor_comments
'Adding full bibliography for 7133436--7133438.cif.'
_cod_original_cell_volume        1493.92(12)
_cod_database_code               7133438
_shelx_shelxl_version_number     2016/4
_chemical_oxdiff_formula         'C H N O'
_chemical_oxdiff_usercomment     14-09-2023
_olex2_refinement_description
;
1. Restrained distances
 C9-C10 \\sim C8-C7 \\sim C6-C5
 with sigma of 0.02
2. Restrained planarity
 C10, C9, C8, C7, C6, C5
 with sigma of 0.1
3. Rigid bond restraints
 C9, C10, C5, C4, C3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C3 \\sim C4 \\sim C5 \\sim C10 \\sim C9: within 1.4A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 1.4A
Uanis(C21) = Uanis(C22) = Uanis(C23)
Uanis(C9) = Uanis(C10)
5. Rigid body (RIGU) restrains
 C9, C10
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C31(H31A,H31B)
6.b Aromatic/amide H refined with riding coordinates:
 C20(H20), C21(H21), C9(H9), C25(H25), C22(H22), C2(H2), C26(H26), C28(H28),
 C27(H27), C6(H6), C4(H4), C8(H8), C3(H3), C7(H7)
6.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C17(H17A,H17B,H17C), C36(H36A,H36B,H36C), C35(H35A,H35B,
 H35C)
;
_shelx_res_checksum              13819
_shelx_hkl_checksum              40013
_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 1.350
_oxdiff_exptl_absorpt_empirical_full_min 0.818