Construction of the Azacyclic Core of Tabernaemontanine-Related Alkaloids via Tandem Reformatsky-Aza-Claisen Rearrangement.
Suh, Young-Ger; Lim, Changjin; Sim, Jaehoon; Lee, Jae Kyun; Surh, Young-Joon; Paek, Seung-Mann; The Journal of organic chemistry 82 (2017) 1464–1470; doi:10.1021/acs.joc.6b02648

data_4032143
_publ_section_title
;
 Construction of the Azacyclic Core of Tabernaemontanine-Related Alkaloids
 via Tandem Reformatsky-Aza-Claisen Rearrangement.
;
_journal_issue                   3
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              1464
_journal_page_last               1470
_journal_paper_doi               10.1021/acs.joc.6b02648
_journal_volume                  82
_journal_year                    2017
_chemical_absolute_configuration unk
_chemical_formula_moiety         '1(C37 H52 N2 O6 Si)'
_chemical_formula_sum            'C37 H52 N2 O6 Si'
_chemical_formula_weight         648.89
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-09-27
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.7738(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.88956(5)
_cell_length_b                   18.75380(7)
_cell_length_c                   15.37317(5)
_cell_measurement_reflns_used    108439
_cell_measurement_temperature    169.91(10)
_cell_measurement_theta_max      76.5660
_cell_measurement_theta_min      4.2540
_cell_volume                     3697.28(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43c (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43c (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43c (Rigaku OD, 2015)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      169.91(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2262
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_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    -66.00  33.00   1.00    1.00    --  -41.24  38.00 120.00   99
  2  \w   -113.00 -13.00   1.00    1.00    --  -41.24 -57.00 -30.00  100
  3  \w     23.00  97.00   1.00    1.00    --   41.24-125.00-180.00   74
  4  \w     30.00 165.00   1.00    3.70    --  112.00 -15.00   0.00  135
  5  \w     29.00 109.00   1.00    3.70    --  112.00 -94.00 150.00   80
  6  \w     36.00 116.00   1.00    3.70    --  112.00-111.00 -90.00   80
  7  \w     84.00 178.00   1.00    3.70    --  112.00  30.00 -30.00   94
  8  \w     86.00 178.00   1.00    3.70    --  112.00  45.00-180.00   92
  9  \w    100.00 178.00   1.00    3.70    --  112.00 111.00-180.00   78
 10  \w     29.00 109.00   1.00    3.70    --  112.00 -94.00-150.00   80
 11  \w   -117.00  -9.00   1.00    1.00    --  -41.24 -77.00 120.00  108
 12  \w   -113.00 -13.00   1.00    1.00    --  -41.24 -57.00-150.00  100
 13  \w      1.00  82.00   1.00    1.00    --   41.24 -99.00 -30.00   81
 14  \w     79.00 178.00   1.00    3.70    --  112.00  77.00 120.00   99
 15  \w     84.00 178.00   1.00    3.70    --  112.00  30.00  90.00   94
 16  \w     23.00  50.00   1.00    4.22    --   41.49  38.00 120.00   27
 17  \w    -25.00   1.00   1.00    4.22    --   41.49 -77.00-150.00   26
 18  \w     11.00  36.00   1.00    4.22    --   46.00  84.00 119.48   25
 19  \w     20.00  45.00   1.00    4.22    --   54.00  81.00 155.01   25
 20  \w     37.00  63.00   1.00    4.22    --   66.00  77.00-109.84   26
 21  \w     36.00  62.00   1.00    4.22    --   66.00  77.00 -93.59   26
 22  \w     38.00  64.00   1.00    4.22    --   66.00  75.00-152.94   26
 23  \w     34.00  60.00   1.00    4.22    --   66.00  77.00 173.12   26
 24  \w     37.00  63.00   1.00    4.22    --   66.00  76.00-139.95   26
 25  \w     35.00  61.00   1.00    4.22    --   66.00  75.00 154.72   26
 26  \w     37.00  62.00   1.00    4.22    --   70.00  77.00-177.86   25
 27  \w     43.00  75.00   1.00    4.22    --   70.00  77.00  78.17   32
 28  \w     43.00  69.00   1.00    4.22    --   74.00  75.00 -71.76   26
 29  \w    141.00 167.00   1.00    3.70    --  112.00  77.00 150.00   26
 30  \w     88.00 115.00   1.00    3.70    --  112.00  45.00 120.00   27
 31  \w     79.00 104.00   1.00    3.70    --  112.00  77.00 150.00   25
 32  \w     79.00 105.00   1.00    3.70    --  112.00  77.00-150.00   26
 33  \w     88.00 114.00   1.00    3.70    --  112.00  45.00-120.00   26
 34  \w     80.00 106.00   1.00    3.70    --  112.00  77.00  60.00   26
 35  \w     79.00 104.00   1.00    3.70    --  112.00  77.00  90.00   25
 36  \w     79.00 105.00   1.00    3.70    --  112.00  77.00-180.00   26
 37  \w     83.00 109.00   1.00    3.70    --  112.00  61.00 150.00   26
 38  \w     84.00 110.00   1.00    3.70    --  112.00  61.00-150.00   26
 39  \w     83.00 109.00   1.00    3.70    --  112.00  61.00-180.00   26
 40  \w     83.00 108.00   1.00    3.70    --  112.00  61.00 120.00   25
 41  \w     88.00 114.00   1.00    3.70    --  112.00  45.00-150.00   26
 42  \w    129.00 155.00   1.00    3.70    --  112.00 111.00 -60.00   26
 43  \w     91.00 117.00   1.00    3.70    --  112.00  45.00 150.00   26
 44  \w     84.00 110.00   1.00    3.70    --  112.00  61.00  90.00   26
 45  \w      6.00  34.00   1.00    4.22    --   42.00  87.00 152.75   28
 46  \w     12.00  40.00   1.00    4.22    --   46.00  83.00 -67.12   28
 47  \w     17.00  46.00   1.00    4.22    --   50.00  80.00   4.27   29
 48  \w     21.00  47.00   1.00    4.22    --   54.00  79.00  54.54   26
 49  \w     20.00  46.00   1.00    4.22    --   54.00  81.00  97.62   26
 50  \w     20.00  46.00   1.00    4.22    --   54.00  81.00-138.13   26
 51  \w     30.00 137.00   1.00    4.22    --   62.00  75.00 134.50  107
 52  \w     33.00 119.00   1.00    4.22    --   66.00  77.00  64.82   86
 53  \w     33.00 142.00   1.00    4.22    --   66.00  77.00-109.84  109
 54  \w     33.00 142.00   1.00    4.22    --   66.00  77.00 -12.83  109
 55  \w     37.00 146.00   1.00    4.22    --   70.00  77.00  78.17  109
 56  \w     42.00 149.00   1.00    4.22    --   74.00  75.00 -71.76  107
 57  \w     41.00 150.00   1.00    4.22    --   74.00  77.00  15.62  109
 58  \w     45.00  75.00   1.00    3.75    --   74.00  72.00-169.67   30
 59  \w     47.00  73.00   1.00    4.86    --   78.00  76.00 154.56   26
 60  \w     52.00  79.00   1.00    4.86    --   82.00  68.00  90.61   27
 61  \w    113.00 138.00   1.00    4.86    --  112.00 -45.00  60.00   25
 62  \w   -116.00 -17.00   1.00    3.75    --  -41.49 -38.00  30.00   99
 63  \w      9.00 118.00   1.00    3.75    --   41.49  77.00-180.00  109
 64  \w     23.00  98.00   1.00    3.75    --   41.49-125.00-180.00   75
 65  \w    -47.00 130.00   1.00    3.75    --   41.49   0.00-180.00  177
 66  \w     13.00 115.00   1.00    3.75    --   41.49  57.00-180.00  102
 67  \w     23.00  98.00   1.00    3.75    --   41.49-125.00 -30.00   75
 68  \w     23.00  98.00   1.00    3.75    --   41.49-125.00-120.00   75
 69  \w    -33.00  66.00   1.00    3.75    --   41.49 -38.00  90.00   99
 70  \w      5.00  33.00   1.00    3.75    --   42.00  89.00 -62.89   28
 71  \w     20.00  46.00   1.00    3.75    --   54.00  81.00-104.43   26
 72  \w     20.00  46.00   1.00    3.75    --   54.00  81.00 -42.11   26
 73  \w     25.00 134.00   1.00    3.75    --   58.00  77.00 -65.41  109
 74  \w     25.00 134.00   1.00    3.75    --   58.00  77.00  91.42  109
 75  \w     26.00 133.00   1.00    3.75    --   58.00  74.00  35.72  107
 76  \w     29.00 138.00   1.00    3.75    --   62.00  77.00 152.39  109
 77  \w     34.00 142.00   1.00    3.75    --   66.00  76.00  34.50  108
 78  \w     34.00 142.00   1.00    3.75    --   66.00  76.00  48.04  108
 79  \w     34.00 142.00   1.00    3.75    --   66.00  76.00  98.92  108
 80  \w     33.00 142.00   1.00    3.75    --   66.00  77.00  20.62  109
 81  \w     33.00 142.00   1.00    3.75    --   66.00  77.00 -67.45  109
 82  \w     37.00 146.00   1.00    3.75    --   70.00  77.00   7.88  109
 83  \w     37.00 146.00   1.00    3.75    --   70.00  77.00 -47.38  109
 84  \w     49.00 148.00   1.00    3.75    --   74.00  41.00 -50.63   99
 85  \w     43.00 148.00   1.00    3.75    --   74.00  72.00-169.67  105
 86  \w     64.00 167.00   1.00    4.86    --   94.00  67.00 -22.36  103
 87  \w     36.00 109.00   1.00    4.86    --  112.00-111.00 120.00   73
 88  \w     79.00 178.00   1.00    4.86    --  112.00  77.00  30.00   99
 89  \w     29.00 109.00   1.00    4.86    --  112.00 -94.00  30.00   80
 90  \w     79.00 178.00   1.00    4.86    --  112.00  77.00-120.00   99
 91  \w     79.00 178.00   1.00    4.86    --  112.00  77.00   0.00   99
 92  \w     36.00 116.00   1.00    4.86    --  112.00-111.00 -30.00   80
 93  \w    -47.00 130.00   1.00    3.75    --   41.49   0.00-150.00  177
 94  \w    -47.00 130.00   1.00    3.75    --   41.49   0.00-120.00  177
 95  \w    -47.00 130.00   1.00    3.75    --   41.49   0.00 -90.00  177
 96  \w    -47.00   5.00   1.00    3.75    --   41.49   0.00 -60.00   52
 97  \w    -47.00 130.00   1.00    3.75    --   41.49   0.00-180.00  177
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1172432000
_diffrn_orient_matrix_UB_12      0.0165709000
_diffrn_orient_matrix_UB_13      -0.0016282000
_diffrn_orient_matrix_UB_21      -0.0125632000
_diffrn_orient_matrix_UB_22      -0.0083260000
_diffrn_orient_matrix_UB_23      -0.1002129000
_diffrn_orient_matrix_UB_31      -0.0229612000
_diffrn_orient_matrix_UB_32      -0.0800175000
_diffrn_orient_matrix_UB_33      0.0100932000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0288
_diffrn_reflns_av_unetI/netI     0.0137
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            151191
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.673
_diffrn_reflns_theta_min         3.446
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.920
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72840
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43c (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.166
_exptl_crystal_description       block
_exptl_crystal_F_000             1400
_exptl_crystal_size_max          0.279
_exptl_crystal_size_mid          0.161
_exptl_crystal_size_min          0.082
_refine_diff_density_max         0.335
_refine_diff_density_min         -0.342
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.01(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     918
_refine_ls_number_reflns         14965
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0479
_refine_ls_R_factor_gt           0.0472
_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^)+(0.0875P)^2^+0.8335P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1245
_refine_ls_wR_factor_ref         0.1254
_reflns_Friedel_coverage         0.872
_reflns_Friedel_fraction_full    0.957
_reflns_Friedel_fraction_max     0.923
_reflns_number_gt                14665
_reflns_number_total             14965
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b02648_si_002.cif
_cod_data_source_block           exp_329
_cod_depositor_comments          'Adding full bibliography for 4032143.cif.'
_cod_database_code               4032143
_chemical_oxdiff_formula         C37H52N2O6Si1
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_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 C(H,H,H) groups
2. Others
 Sof(Si)=Sof(C1)=Sof(C2AA)=Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=Sof(C3)=Sof(H3A)=
 Sof(H3B)=Sof(H3C)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C6A)=Sof(H6AA)=
 Sof(H6AB)=Sof(H6AC)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=1-FVAR(1)
 Sof(Si00)=Sof(C0AA)=Sof(C1AA)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C3AA)=
 Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C6)=
 Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C00M(H00M), C00U(H00U), C01B(H01B), C00P(H00P), C01F(H01N), C014(H014)
3.b Secondary CH2 refined with riding coordinates:
 C01C(H01A,H01C), C01H(H01D,H01E), C01R(H01F,H01G), C015(H01H,H01J), C01L(H01S,
 H01T), C01M(H01U,H01V), C01N(H01X,H01Y), C013(H7AA,HD)
3.c Aromatic/amide H refined with riding coordinates:
 N00G(H00G), C01I(H01I), C01K(H01K), C01O(H01O), C01P(H01P), C01Q(H01Q),
 C01W(H01W), C011(H011), C018(H018), C019(H019), C025(H025), N00E(H00E),
 C00Y(H00Y), C01A(H01L), C01E(H01M), C01G(H01R), C01S(H01Z), C01U(H01),
 C01V(H0AA), C01X(H4AA), C010(H010), C017(H017)
3.d Idealised Me refined as rotating group:
 C1AA(H1AA,H1AB,H1AC), C2AA(H2AA,H2AB,H2AC), C02C(H02A,H02B,H02C), C3(H3A,H3B,
 H3C), C3AA(H3AA,H3AB,H3AC), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C),
 C6A(H6AA,H6AB,H6AC), C9(H9A,H9B,H9C), C12(H12A,H12B,H12C), C020(H02D,H02E,
 H02F), C021(H02G,H02H,H02I), C022(H02J,H02K,H02L), C023(H02M,H02N,H02O),
 C01Y(H5AA,H,HA), C02A(H02P,H02Q,H02R), C02D(H02S,H02T,H02U), C02E(H02V,H02W,
 H02X), C02F(H02Y,HB,HC), C024(H02Z,HE,HF), C026(H02,HG,HH), C027(H8AA,HI,HJ),
 C028(H9AA,HK,HL), C029(H0BA,HM,HN)
;
_shelx_res_checksum              30015
_shelx_hkl_checksum              85395
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-05-16
_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 1.751
_oxdiff_exptl_absorpt_empirical_full_min 0.763