Continuous Flow Synthesis of Morpholines and Oxazepanes with Silicon Amine Protocol (SLAP) Reagents and Lewis Acid Facilitated Photoredox Catalysis.
Jackl, Moritz K.; Legnani, Luca; Morandi, Bill; Bode, Jeffrey W.; Organic letters 19 (2017) 4696–4699; doi:10.1021/acs.orglett.7b02395

data_1547011
_publ_section_title
;
 Continuous Flow Synthesis of Morpholines and Oxazepanes with Silicon
 Amine Protocol (SLAP) Reagents and Lewis Acid Facilitated Photoredox
 Catalysis.
;
_journal_issue                   17
_journal_name_full               'Organic letters'
_journal_page_first              4696
_journal_page_last               4699
_journal_paper_doi               10.1021/acs.orglett.7b02395
_journal_volume                  19
_journal_year                    2017
_chemical_formula_moiety         'C18 H17 F N2 O'
_chemical_formula_sum            'C18 H17 F N2 O'
_chemical_formula_weight         296.33
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-04-25
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.811(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   35.2170(7)
_cell_length_b                   5.77170(10)
_cell_length_c                   14.5002(2)
_cell_measurement_reflns_used    18584
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      78.6240
_cell_measurement_theta_min      9.8370
_cell_volume                     2884.94(9)
_computing_cell_refinement       'CrysAlisPro 1.171.39.8d (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.8d (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.8d (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 300K'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.990
_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    -91.00  -6.00   0.50   12.00    --  -70.00  77.00  90.00  170
  2  \w   -139.00 -71.00   0.50   12.00    --  -70.00-125.00  90.00  136
  3  \w    -76.00   4.00   0.50   12.00    --  -70.00  19.00-150.00  160
  4  \w     44.00 129.00   0.50   12.00    --  107.75 -77.00   0.00  170
  5  \w     38.00 106.00   0.50   12.00    --  107.75 -57.00-150.00  136
  6  \w     40.00 110.00   0.50   12.00    --  107.75 -99.00 -30.00  140
  7  \w     99.00 177.00   0.50   12.00    --  107.75  38.00 150.00  156
  8  \w     98.00 177.00   0.50   12.00    --  107.75  19.00-120.00  158
  9  \w     40.00 110.00   0.50   12.00    --  107.75 -99.00-180.00  140
 10  \w     86.00 172.00   0.50   12.00    --  107.75  77.00  90.00  172
 11  \w   -134.00 -49.00   0.50   12.00    --  -70.00 -77.00-150.00  170
 12  \w   -140.00 -56.00   0.50   12.00    --  -70.00 -57.00-120.00  168
 13  \w   -134.00 -49.00   0.50   12.00    --  -70.00 -77.00 -60.00  170
 14  \w   -134.00 -49.00   0.50   12.00    --  -70.00 -77.00 150.00  170
 15  \w   -134.00 -49.00   0.50   12.00    --  -70.00 -77.00   0.00  170
 16  \w   -134.00 -49.00   0.50   12.00    --  -70.00 -77.00  90.00  170
 17  \w     34.00  76.00   0.50   12.00    --  107.75 -19.00  60.00   84
 18  \w     98.00 177.00   0.50   12.00    --  107.75  19.00  30.00  158
 19  \w   -134.00 -97.00   0.50   12.00    --  -70.00 -77.00-180.00   74
 20  \w   -134.00 -49.00   0.50   12.00    --  -70.00 -77.00  60.00  170
 21  \w     94.00 177.00   0.50   12.00    --  107.75  57.00  60.00  166
 22  \w     34.00  70.00   0.50   12.00    --  107.75 -38.00 150.00   72
 23  \w     34.00  70.00   0.50   12.00    --  107.75 -38.00 -60.00   72
 24  \w     34.00  70.00   0.50   12.00    --  107.75 -38.00  60.00   72
 25  \w     34.00  76.00   0.50   12.00    --  107.75 -19.00 -30.00   84
 26  \w     86.00 172.00   0.50   12.00    --  107.75  77.00 -60.00  172
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 300K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0397082000
_diffrn_orient_matrix_UB_12      0.0498981000
_diffrn_orient_matrix_UB_13      -0.0247850000
_diffrn_orient_matrix_UB_21      0.0204971000
_diffrn_orient_matrix_UB_22      -0.1045067000
_diffrn_orient_matrix_UB_23      0.0949401000
_diffrn_orient_matrix_UB_31      -0.0006701000
_diffrn_orient_matrix_UB_32      -0.2404843000
_diffrn_orient_matrix_UB_33      -0.0464058000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0477
_diffrn_reflns_av_unetI/netI     0.0283
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       42
_diffrn_reflns_limit_h_min       -42
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            42190
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.073
_diffrn_reflns_theta_min         9.423
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.770
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78333
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.8d (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.365
_exptl_crystal_description       plate
_exptl_crystal_F_000             1248
_exptl_crystal_size_max          0.144
_exptl_crystal_size_mid          0.097
_exptl_crystal_size_min          0.019
_refine_diff_density_max         0.228
_refine_diff_density_min         -0.195
_refine_diff_density_rms         0.039
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     406
_refine_ls_number_reflns         5396
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0390
_refine_ls_R_factor_gt           0.0350
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0547P)^2^+0.7760P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0917
_refine_ls_wR_factor_ref         0.0940
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4965
_reflns_number_total             5396
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b02395_si_001.cif
_cod_data_source_block           jb020317_4_1
_cod_database_code               1547011
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C18 H17 F N2 O'
_diffrn_oxdiff_ac3_digest_frames
;
01c637c73695ce83ba992f0c5f139eacc203680c0d1
;
_diffrn_oxdiff_ac3_digest_hkl
;
010dffb33d55839d35388f374b1b9e6e4885ba
;
_reflns_odcompleteness_completeness 99.12
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.731(1)
 0.269(1)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 N2-H2 = N1-H1
 0.93 with sigma of 0.02
4.a Ternary CH refined with riding coordinates:
 C20(H20), C18(H18)
4.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C26(H26A,H26B), C19(H19A,H19B), C31(H31A,H31B)
4.c Aromatic/amide H refined with riding coordinates:
 C2(H2A), C8(H8), C10(H10), C25(H25), C28(H28), C29(H29), C32(H32), C34(H34),
 C1(H1A), C9(H9), C12(H12), C24(H24), C30(H30), C33(H33), C35(H35), C36(H36)
4.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              37855
_shelx_hkl_checksum              67874
_olex2_date_sample_data_collection 2017-04-05
_olex2_date_sample_submission    2017-04-22
_olex2_submission_original_sample_id jb020317_4_1
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.377
_oxdiff_exptl_absorpt_empirical_full_min 0.735