Transition Metal-Free Selective Double sp(3) C-H Oxidation of Cyclic Amines to 3-Alkoxyamine Lactams.
Osorio-Nieto, Urbano; Chamorro-Arenas, Delfino; Quintero, Leticia; Höpfl, Herbert; Sartillo-Piscil, Fernando; The Journal of organic chemistry 81 (2016) 8625–8632; doi:10.1021/acs.joc.6b01566

data_4037127
_publ_section_title
;
 Transition Metal-Free Selective Double sp(3) C-H Oxidation of Cyclic
 Amines to 3-Alkoxyamine Lactams.
;
_journal_issue                   18
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              8625
_journal_page_last               8632
_journal_paper_doi               10.1021/acs.joc.6b01566
_journal_volume                  81
_journal_year                    2016
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C21 H32 N2 O3'
_chemical_formula_sum            'C21 H32 N2 O3'
_chemical_formula_weight         360.48
_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     direct
_audit_creation_date             2015-09-18
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.104(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.8941(5)
_cell_length_b                   8.3839(4)
_cell_length_c                   11.3210(5)
_cell_measurement_reflns_used    4115
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      28.5800
_cell_measurement_theta_min      3.4180
_cell_volume                     1020.98(8)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0769
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega   -4.00   80.00   1.0000    2.8600
omega____ theta____ kappa____ phi______ frames
    -       15.2374   38.0000  -90.0000 84

  2 omega   56.00   81.00   1.0000    2.8600
omega____ theta____ kappa____ phi______ frames
    -       15.2374   57.0000  -90.0000 25

  3 omega   39.00   67.00   1.0000    2.8600
omega____ theta____ kappa____ phi______ frames
    -       15.2374  178.0000   90.0000 28

  4 omega  -54.00   85.00   1.0000    2.8600
omega____ theta____ kappa____ phi______ frames
    -       15.2374    0.0000 -150.0000 139

  5 omega   13.00   47.00   1.0000    2.8600
omega____ theta____ kappa____ phi______ frames
    -       15.2374  -99.0000  -90.0000 34

  6 omega  -49.00   -1.00   1.0000    2.8600
omega____ theta____ kappa____ phi______ frames
    -       15.2374  -57.0000 -150.0000 48
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0564793000
_diffrn_orient_matrix_UB_12      -0.0274577000
_diffrn_orient_matrix_UB_13      0.0165009000
_diffrn_orient_matrix_UB_21      0.0320009000
_diffrn_orient_matrix_UB_22      -0.0204764000
_diffrn_orient_matrix_UB_23      0.0575379000
_diffrn_orient_matrix_UB_31      -0.0115862000
_diffrn_orient_matrix_UB_32      0.0773452000
_diffrn_orient_matrix_UB_33      0.0211007000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0234
_diffrn_reflns_av_unetI/netI     0.0421
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            6860
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.994
_diffrn_reflns_theta_max         24.994
_diffrn_reflns_theta_min         2.828
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.078
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77088
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'translucent colourless'
_exptl_crystal_density_diffrn    1.173
_exptl_crystal_description       prism
_exptl_crystal_F_000             392
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.125
_refine_diff_density_min         -0.189
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 1366 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.7(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     240
_refine_ls_number_reflns         3589
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0422
_refine_ls_R_factor_gt           0.0391
_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^)+(0.0390P)^2^+0.1013P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0844
_refine_ls_wR_factor_ref         0.0866
_reflns_Friedel_coverage         0.862
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                3371
_reflns_number_total             3589
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b01566_si_003.cif
_cod_data_source_block           sferein
_cod_original_cell_volume        1020.97(8)
_cod_database_code               4037127
_chemical_oxdiff_formula         'C H N O'
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C2(H2), C4(H4)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B), C14(H14A,H14B), C15(H15A,H15B),
 C16(H16A,H16B)
2.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C12(H12)
2.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C)
2.e Idealised tetrahedral OH refined as rotating group:
 O3(H3)
;
_shelx_res_checksum              55059
_shelx_hkl_checksum              40327
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'