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_7133437
_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_absolute_configuration ad
_chemical_formula_moiety         'C19 H15 N O3'
_chemical_formula_sum            'C19 H15 N O3'
_chemical_formula_weight         305.32
_chemical_name_systematic        SMT-238
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-04-24
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-04-24 deposited with the CCDC.	2024-07-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 112.449(6)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.2750(5)
_cell_length_b                   6.3644(3)
_cell_length_c                   12.1715(6)
_cell_measurement_reflns_used    4418
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      29.9740
_cell_measurement_theta_min      3.4490
_cell_volume                     735.63(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.69a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.69a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.69a (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_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_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  76.00   0.50    1.33    --    5.83  23.00 115.00  146
  2  \w      6.00  32.00   0.50    1.33    --    5.83  38.00 -60.00   52
  3  \w     35.00  61.00   0.50    1.33    --    5.83  38.00 -60.00   52
  4  \w      1.00  79.00   0.50    1.33    --    5.83  38.00-180.00  156
  5  \w    -35.00  18.00   0.50    1.33    --    5.83 -23.00 -49.00  106
  6  \w    -67.00 -42.00   0.50    1.33    --    5.83 -23.00 -49.00   50
  7  \w    -17.00   9.00   0.50    1.33    --   -5.68 -99.00  90.00   52
;
_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      -0.0633302000
_diffrn_orient_matrix_UB_12      -0.0284544000
_diffrn_orient_matrix_UB_13      -0.0475052000
_diffrn_orient_matrix_UB_21      -0.0326476000
_diffrn_orient_matrix_UB_22      -0.0178991000
_diffrn_orient_matrix_UB_23      0.0410388000
_diffrn_orient_matrix_UB_31      -0.0224894000
_diffrn_orient_matrix_UB_32      0.1062453000
_diffrn_orient_matrix_UB_33      -0.0058392000
_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  0.0310
_diffrn_reflns_av_unetI/netI     0.0364
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            7187
_diffrn_reflns_point_group_measured_fraction_full 0.967
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.356
_diffrn_reflns_theta_min         3.294
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.094
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81656
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.69a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear whiteish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.378
_exptl_crystal_description       needle
_exptl_crystal_F_000             320
_refine_diff_density_max         0.193
_refine_diff_density_min         -0.161
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 1069 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.1(7)
_refine_ls_extinction_coef       0.010(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/4 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     210
_refine_ls_number_reflns         2879
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0390
_refine_ls_R_factor_gt           0.0355
_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^)+(0.0323P)^2^+0.1490P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0813
_refine_ls_wR_factor_ref         0.0832
_reflns_Friedel_coverage         0.755
_reflns_Friedel_fraction_full    0.929
_reflns_Friedel_fraction_max     0.911
_reflns_number_gt                2686
_reflns_number_total             2879
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc02639j2.cif
_cod_data_source_block           smt-238_auto
_cod_depositor_comments
'Adding full bibliography for 7133436--7133438.cif.'
_cod_database_code               7133437
_shelx_shelxl_version_number     2016/4
_chemical_oxdiff_formula         'C H N O I'
_chemical_oxdiff_usercomment     18-04-2023
_reflns_odcompleteness_completeness 99.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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 Secondary CH2 refined with riding coordinates:
 C00M(H00K,H00L)
2.b Aromatic/amide H refined with riding coordinates:
 C006(H006), C008(H008), C00D(H00D), C00E(H00E), C00F(H00F), C00G(H00G),
 C00H(H00H), C00I(H00I), C00J(H00J), C00N(H00N)
2.c Idealised Me refined as rotating group:
 C00L(H00A,H00B,H00C)
;
_shelx_res_checksum              33010
_shelx_hkl_checksum              35797
_olex2_submission_original_sample_id SMT-238
_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 1.513
_oxdiff_exptl_absorpt_empirical_full_min 0.776