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_4037126
_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                 96.501(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.5796(4)
_cell_length_b                   10.5928(3)
_cell_length_c                   16.6027(6)
_cell_measurement_reflns_used    7847
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      28.6630
_cell_measurement_theta_min      3.7250
_cell_volume                     2023.40(12)
_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  -54.00   81.00   1.0000    4.9950
omega____ theta____ kappa____ phi______ frames
    -       15.2374    0.0000   30.0000 135

  2 omega    8.00   54.00   1.0000    4.9950
omega____ theta____ kappa____ phi______ frames
    -       15.2374  -99.0000  -60.0000 46

  3 omega  -51.00   17.00   1.0000    4.9950
omega____ theta____ kappa____ phi______ frames
    -       15.2374  -57.0000    0.0000 68

  4 omega  -71.00  -13.00   1.0000    4.9950
omega____ theta____ kappa____ phi______ frames
    -      -16.1749  -38.0000  -30.0000 58

  5 omega  -58.00  -11.00   1.0000    4.9950
omega____ theta____ kappa____ phi______ frames
    -      -16.1749  110.0000  109.0000 47

  6 omega   43.00   71.00   1.0000    4.9950
omega____ theta____ kappa____ phi______ frames
    -       15.2374  178.0000  -60.0000 28
;
_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      -0.0462084000
_diffrn_orient_matrix_UB_12      -0.0362935000
_diffrn_orient_matrix_UB_13      -0.0198771000
_diffrn_orient_matrix_UB_21      0.0247028000
_diffrn_orient_matrix_UB_22      0.0056955000
_diffrn_orient_matrix_UB_23      -0.0370112000
_diffrn_orient_matrix_UB_31      0.0324915000
_diffrn_orient_matrix_UB_32      -0.0559949000
_diffrn_orient_matrix_UB_33      0.0091279000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0282
_diffrn_reflns_av_unetI/netI     0.0470
_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       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            14396
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         2.614
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.079
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84105
_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    1.183
_exptl_crystal_description       prism
_exptl_crystal_F_000             784
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.226
_refine_diff_density_min         -0.241
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details
;
 Flack x determined using 2789 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.1(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.107
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     479
_refine_ls_number_reflns         7147
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.107
_refine_ls_R_factor_all          0.0506
_refine_ls_R_factor_gt           0.0471
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0460P)^2^+1.2378P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1174
_refine_ls_wR_factor_ref         0.1195
_reflns_Friedel_coverage         0.889
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                6700
_reflns_number_total             7147
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b01566_si_002.cif
_cod_data_source_block           sferzwe
_cod_database_code               4037126
_chemical_oxdiff_formula         'C H NO'
_chemical_oxdiff_usercomment     'C H O N '
_reflns_odcompleteness_completeness 99.84
_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), C32(H32), C34(H34)
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), C33(H33A,H33B), C35(H35A,H35B), C36(H36A,H36B), C44(H44A,H44B),
  C45(H45A,H45B), C46(H46A,H46B)
2.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C38(H38), C39(H39), C40(H40),
 C41(H41), C42(H42)
2.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C51(H51A,
 H51B,H51C)
2.e Idealised tetrahedral OH refined as rotating group:
 O3(H3), O33(H33)
;
_shelx_res_checksum              54681
_shelx_hkl_checksum              18529
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'