Oxone-DMSO Triggered Methylene Insertion and C(sp<sup>2</sup>)-C(sp<sup>3</sup>)-H-C(sp<sup>2</sup>) Bond Formation to Access Functional Bis-Heterocycles.
Kour, Jaspreet; Venkateswarlu, Vunnam; Verma, Praveen K.; Hussain, Yaseen; Dubey, Gurudutt; Bharatam, Prasad V.; Sahoo, Subash C.; Sawant, Sanghapal D.; The Journal of organic chemistry 85 (2020) 4951–4962; doi:10.1021/acs.joc.9b03477

data_4038064
_publ_section_title
;
 Oxone-DMSO Triggered Methylene Insertion and
 C(sp<sup>2</sup>)-C(sp<sup>3</sup>)-H-C(sp<sup>2</sup>) Bond Formation to
 Access Functional Bis-Heterocycles.
;
_journal_issue                   7
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              4951
_journal_page_last               4962
_journal_paper_doi               10.1021/acs.joc.9b03477
_journal_volume                  85
_journal_year                    2020
_chemical_formula_moiety         'C22 H22 Br N5'
_chemical_formula_sum            'C22 H22 Br N5'
_chemical_formula_weight         436.35
_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
_audit_creation_date             2019-04-01
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.02.24 svn.r3390 for Rigaku Oxford Diffraction, GUI svn.r5318)
;
_cell_angle_alpha                90
_cell_angle_beta                 106.145(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.7052(2)
_cell_length_b                   48.2715(12)
_cell_length_c                   7.5578(2)
_cell_measurement_reflns_used    12157
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      26.6670
_cell_measurement_theta_min      3.2710
_cell_volume                     1999.32(11)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.946
_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    -38.00 -11.78   0.38   10.00    --   -9.95 113.00  16.00   69
  2  \w      6.00  48.18   0.38   10.00    --   10.22-113.00 -75.00  111
  3  \w    -74.00   6.18   0.38   10.00    --   -9.95 -77.00  30.00  211
  4  \w    -80.00   0.18   0.38   10.00    --   -9.95 -19.00-120.00  211
  5  \w    -22.00   4.22   0.38   10.00    --   -9.95  38.00-150.00   69
  6  \w    -35.00  -6.88   0.38   10.00    --   10.22 120.00-152.70   74
  7  \w      7.00  42.34   0.38   10.00    --   10.22 -99.00-150.00   93
  8  \w    -18.00  39.00   0.38   10.00    --   10.22 -99.00 -60.00  150
  9  \w     20.00  58.00   0.38   10.00    --   10.22-125.00-180.00  100
 10  \w      3.00  58.10   0.38   10.00    --   10.22-125.00  30.00  145
 11  \w    -53.00  23.00   0.38   10.00    --   10.22 -38.00-180.00  200
 12  \w    -37.00  -7.74   0.38   10.00    --   10.22 130.00 -50.18   77
 13  \w    -19.00   9.12   0.38   10.00    --   10.22 -99.00 150.00   74
 14  \w    -42.00 -13.88   0.38   10.00    --   10.22 -19.00  30.00   74
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0504
_diffrn_reflns_av_unetI/netI     0.0432
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.946
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       55
_diffrn_reflns_limit_k_min       -62
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            23405
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.453
_diffrn_reflns_theta_min         3.275
_diffrn_source                   'microfocus sealed tube X-ray'
_diffrn_source_type              'spernova (Mo) X-ray'
_exptl_absorpt_coefficient_mu    2.074
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49192
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colurless
_exptl_crystal_density_diffrn    1.450
_exptl_crystal_description       rod
_exptl_crystal_F_000             896
_exptl_crystal_recrystallization_method 'slow evaporation'
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.254
_refine_diff_density_min         -0.320
_refine_diff_density_rms         0.050
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     293
_refine_ls_number_reflns         4338
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0696
_refine_ls_R_factor_gt           0.0457
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0316P)^2^+1.2990P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0878
_refine_ls_wR_factor_ref         0.0949
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3294
_reflns_number_total             4338
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b03477_si_001.cif
_cod_data_source_block           sub-kas-csir
_cod_depositor_comments          'Adding full bibliography for 4038064.cif.'
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               4038064
_shelx_shelxl_version_number     2018/3
_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. Others
 Fixed Sof: C18(0.5) H18(0.5) C19(0.5) H19(0.5) C21(0.5) H21(0.5) C22(0.5)
 H22(0.5) C18A(0.5) H18A(0.5) C19A(0.5) H19A(0.5) C21A(0.5) H21A(0.5) C22A(0.5)
 H22A(0.5)
3.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B)
3.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C4(H4), C3(H3), C2(H2), C18(H18), C19(H19), C21(H21), C22(H22),
 C18A(H18A), C19A(H19A), C21A(H21A), C22A(H22A)
3.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C10(H10A,H10B,H10C), C9(H9A,H9B,H9C)
;
_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
;