Main-Group-Catalyzed Reductive Alkylation of Multiply Substituted Amines with Aldehydes Using H<sub>2</sub>.
Hoshimoto, Yoichi; Kinoshita, Takuya; Hazra, Sunit; Ohashi, Masato; Ogoshi, Sensuke; Journal of the American Chemical Society 140 (2018) 7292–7300; doi:10.1021/jacs.8b03626

data_4132389
_publ_section_title
;
 Main-Group-Catalyzed Reductive Alkylation of Multiply Substituted Amines
 with Aldehydes Using H<sub>2</sub>.
;
_journal_issue                   23
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              7292
_journal_page_last               7300
_journal_paper_doi               10.1021/jacs.8b03626
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C15 H13 N O4'
_chemical_formula_sum            'C15 H13 N O4'
_chemical_formula_weight         271.27
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_atom_sites_solution_primary     dual
_audit_creation_date             2017-10-30
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                64.760(6)
_cell_angle_beta                 79.688(5)
_cell_angle_gamma                86.397(5)
_cell_formula_units_Z            2
_cell_length_a                   7.7110(5)
_cell_length_b                   10.5200(6)
_cell_length_c                   10.5887(6)
_cell_measurement_reflns_used    4119
_cell_measurement_temperature    128
_cell_measurement_theta_max      73.0160
_cell_measurement_theta_min      4.6560
_cell_volume                     764.31(9)
_computing_cell_refinement       'CrysAlisPro 1.171.39.31d (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.31d (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.31d (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'ShelXD (Sheldrick, 2008)'
_diffrn_ambient_temperature      128
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.9644
_diffrn_measured_fraction_theta_max 0.9644
_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     22.00 115.00   0.50    1.15    --   42.80  57.00 150.00  186
  2  \w    103.00 129.00   0.50    4.60    --   76.50 123.00  73.00   52
  3  \w     71.00  96.00   0.50    1.15    --   42.80 125.00 -30.00   50
  4  \w     58.00  98.00   0.50    1.15    --   42.80 148.00-122.00   80
  5  \w     74.00 116.00   0.50    1.15    --   42.80 125.00-150.00   84
  6  \w     79.00 104.00   0.50    4.60    --   76.50 148.00-122.00   50
  7  \w     58.00 134.00   0.50    4.60    --   76.50  37.00-150.00  152
  8  \w     33.00  76.00   0.50    1.15    --   42.80-123.00  -6.00   86
  9  \w     64.00  90.00   0.50    4.60    --   76.50-123.00  -6.00   52
 10  \w     42.00  67.00   0.50    1.15    --   42.80-148.00-170.00   50
 11  \w     54.00  94.00   0.50    4.60    --   76.50-148.00-170.00   80
 12  \w    -51.00 -26.00   0.50    1.15    --  -42.80 123.00  73.00   50
 13  \w    -83.00 -57.00   0.50    4.60    -- -106.00 125.00  90.00   52
 14  \w   -105.00 -73.00   0.50    4.60    -- -106.00 123.00  73.00   64
 15  \w   -109.00 -34.00   0.50    4.60    -- -106.00  57.00  90.00  150
 16  \w   -120.00 -31.00   0.50    4.60    -- -106.00  37.00 -60.00  178
 17  \w   -109.00 -66.00   0.50    1.15    --  -42.80 148.00-122.00   86
 18  \w   -113.00 -63.00   0.50    1.15    --  -42.80-148.00-170.00  100
 19  \w   -117.00 -80.00   0.50    4.60    -- -106.00-148.00-170.00   74
 20  \w   -141.00-115.00   0.50    4.60    -- -106.00-123.00  -6.00   52
 21  \w   -138.00 -83.00   0.50    4.60    -- -106.00 -37.00  60.00  110
 22  \w   -127.00 -35.00   0.50    4.60    -- -106.00  37.00  90.00  184
 23  \w   -118.00 -93.00   0.50    4.60    -- -106.00 125.00 -30.00   50
 24  \w   -127.00 -82.00   0.50    4.60    -- -106.00 148.00-122.00   90
 25  \w   -120.00 -33.00   0.50    4.60    -- -106.00 125.00-120.00  174
 26  \w   -117.00 -36.00   0.50    4.60    -- -106.00  37.00-150.00  162
 27  \w   -119.00 -90.00   0.50    4.60    -- -106.00 125.00-180.00   58
 28  \w   -121.00 -55.00   0.50    4.60    -- -106.00  77.00-180.00  132
 29  \w   -121.00 -34.00   0.50    4.60    -- -106.00  57.00 -60.00  174
 30  \w   -136.00 -55.00   0.50    4.60    -- -106.00  19.00 120.00  162
 31  \w   -109.00 -70.00   0.50    1.15    --  -42.80-125.00 150.00   78
 32  \w   -166.00-104.00   0.50    4.60    -- -106.00 -57.00 150.00  124
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0922266000
_diffrn_orient_matrix_UB_12      0.1344112000
_diffrn_orient_matrix_UB_13      -0.0892948000
_diffrn_orient_matrix_UB_21      0.1590289000
_diffrn_orient_matrix_UB_22      0.0890705000
_diffrn_orient_matrix_UB_23      -0.0131344000
_diffrn_orient_matrix_UB_31      0.0863135000
_diffrn_orient_matrix_UB_32      -0.0147180000
_diffrn_orient_matrix_UB_33      -0.1359497000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0246
_diffrn_reflns_av_unetI/netI     0.0282
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            7795
_diffrn_reflns_theta_full        73.9731
_diffrn_reflns_theta_max         73.97
_diffrn_reflns_theta_min         4.65
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.719
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78705
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.31d (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.1786
_exptl_crystal_description       plate
_exptl_crystal_F_000             285.0202
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.6619
_refine_diff_density_min         -0.3997
_refine_diff_density_rms         0.0762
_refine_ls_d_res_high            0.8021
_refine_ls_d_res_low             9.5146
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.2819
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    25
_refine_ls_number_parameters     184
_refine_ls_number_reflns         2981
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.2819
_refine_ls_R_factor_all          0.0711
_refine_ls_R_factor_gt           0.0660
_refine_ls_shift/su_max          0.0008
_refine_ls_shift/su_mean         0.0002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2731
_refine_ls_wR_factor_ref         0.2814
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              9
_reflns_limit_h_min              -9
_reflns_limit_k_max              13
_reflns_limit_k_min              -11
_reflns_limit_l_max              13
_reflns_limit_l_min              0
_reflns_number_gt                2621
_reflns_number_total             2981
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            ja8b03626_si_002.cif
_cod_data_source_block           4au
_cod_original_cell_volume        764.32(9)
_cod_database_code               4132389
_chemical_oxdiff_formula         'C15 H17 N1 O6 '
_reflns_odcompleteness_completeness 99.78
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. 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 O(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C014(H01a,H01b)
2.b Aromatic/amide H refined with riding coordinates:
 C011(H011), C012(H012), C007(H007), C018(H018), C021(H021), C1(H1a),
 C019(H019), C016(H016), N1(H1)
2.c Idealised tetrahedral OH refined as rotating group:
 O001(H001), O002(H002)
;
_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 1.957
_oxdiff_exptl_absorpt_empirical_full_min 0.722