A Total Synthesis of (±)-3-O-Demethylmacronine through Rearrangement of a Precursor Embodying the Haemanthidine Alkaloid Framework.
Ma, Xiang; Gao, Nadia; Banwell, Martin G.; Carr, Paul D.; Willis, Anthony C.; The Journal of organic chemistry 82 (2017) 4336–4341; doi:10.1021/acs.joc.7b00340

data_4032454
_publ_section_title
;
 A Total Synthesis of (+-)-3-O-Demethylmacronine through Rearrangement of
 a Precursor Embodying the Haemanthidine Alkaloid Framework.
;
_journal_issue                   8
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              4336
_journal_page_last               4341
_journal_paper_doi               10.1021/acs.joc.7b00340
_journal_volume                  82
_journal_year                    2017
_chemical_formula_sum            'C23 H31 Cl2 N O5 Si'
_chemical_formula_weight         500.48
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-11-16
_audit_creation_method           'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_audit_update_record
;
2016-11-30 # Formatted by publCIF

;
_cell_angle_alpha                90.0
_cell_angle_beta                 103.2764(7)
_cell_angle_gamma                90.0
_cell_formula_units_Z            4
_cell_length_a                   6.24090(5)
_cell_length_b                   50.3641(3)
_cell_length_c                   8.25660(6)
_cell_measurement_reflns_used    22139
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.8370
_cell_measurement_theta_min      3.5000
_cell_volume                     2525.83(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'SHELXLE (C. B.  H\"bschle et al.,2011)'
_computing_publication_material  'publCIF (Westrip, 2010)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.9896
_diffrn_measured_fraction_theta_max 0.9990
_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   -105.00 -10.80   0.30    0.30    --  -36.95 -77.00 120.00  314
  2  \w    -54.00  30.00   0.30    0.30    --  -36.95  57.00-120.00  280
  3  \w   -104.00 -20.00   0.30    0.30    --  -36.95 -57.00   0.00  280
  4  \w      8.00 107.00   0.30    0.30    --   36.95  19.00-120.00  330
  5  \w      1.00  26.20   0.30    0.30    --   36.95  93.00 105.75   84
  6  \w     20.00 104.00   0.30    0.30    --   36.95  57.00 -60.00  280
  7  \w    -31.00  63.20   0.30    0.30    --   36.95 -77.00  90.00  314
  8  \w    -31.00  63.20   0.30    0.30    --   36.95 -77.00  60.00  314
  9  \w      8.00 107.00   0.30    0.30    --   36.95  19.00   0.00  330
 10  \w     23.00  89.00   0.30    0.30    --   36.95-125.00 150.00  220
 11  \w     23.00  89.00   0.30    0.30    --   36.95-125.00-120.00  220
 12  \w      1.00  76.00   0.30    0.30    --   36.95 -99.00   0.00  250
 13  \w    -32.00  55.00   0.30    0.30    --   36.95 -38.00 150.00  290
 14  \w     42.00 145.20   0.30    0.30    --  111.00 -92.00-180.00  344
 15  \w     41.00 116.00   0.30    0.30    --  111.00-111.00  90.00  250
 16  \w     43.00 127.00   0.30    0.30    --  111.00 -50.00   0.00  280
 17  \w     41.00 135.20   0.30    0.30    --  111.00 -25.00 120.00  314
 18  \w     43.00 127.00   0.30    0.30    --  111.00 -50.00 -90.00  280
 19  \w     44.00 131.00   0.30    0.30    --  111.00 -64.00-180.00  290
 20  \w     41.00 177.20   0.30    0.30    --  111.00  -5.00  54.09  454
 21  \w     41.00 116.00   0.30    0.30    --  111.00-111.00 150.00  250
 22  \w     41.00 135.20   0.30    0.30    --  111.00 -25.00-180.00  314
 23  \w     42.00 129.00   0.30    0.30    --  111.00 -38.00-150.00  290
 24  \w     41.00 135.20   0.30    0.30    --  111.00 -25.00 -90.00  314
 25  \w     43.00 137.20   0.30    0.30    --  111.00 -77.00  90.00  314
 26  \w     86.00 177.20   0.30    0.30    --  111.00  25.00  30.00  304
 27  \w     94.00 178.00   0.30    0.30    --  111.00  50.00 150.00  280
 28  \w     44.00 131.00   0.30    0.30    --  111.00 -64.00-150.00  290
 29  \w     42.00 129.00   0.30    0.30    --  111.00 -38.00-120.00  290
 30  \w     41.00 116.00   0.30    0.30    --  111.00-111.00  30.00  250
 31  \w     41.00 116.00   0.30    0.30    --  111.00-111.00-120.00  250
 32  \w     42.00 129.00   0.30    0.30    --  111.00 -38.00 150.00  290
 33  \w     43.00 137.20   0.30    0.30    --  111.00 -77.00   0.00  314
 34  \w     94.00 178.00   0.30    0.30    --  111.00  50.00  90.00  280
 35  \w    100.00 178.00   0.30    0.30    --  111.00 111.00-150.00  260
 36  \w     43.00 127.00   0.30    0.30    --  111.00 -50.00  90.00  280
 37  \w     92.00 177.20   0.30    0.30    --  111.00  38.00-180.00  284
 38  \w     41.00 116.00   0.30    0.30    --  111.00-111.00-180.00  250
 39  \w     43.00 127.00   0.30    0.30    --  111.00 -50.00 150.00  280
 40  \w     41.00 116.00   0.30    0.30    --  111.00-111.00  60.00  250
 41  \w    118.00 144.10   0.30    0.30    --  111.00  38.00-150.00   87
 42  \w     94.00 157.00   0.30    0.30    --  111.00  50.00 120.00  210
 43  \w     51.00 106.20   0.30    0.30    --  111.00 -64.00  90.00  184
 44  \w     87.00 126.00   0.30    0.30    --  111.00  25.00  90.00  130
 45  \w    138.00 164.10   0.30    0.30    --  111.00  25.00  90.00   87
 46  \w     63.00  90.00   0.30    0.30    --  111.00 -77.00 -30.00   90
 47  \w    100.00 125.50   0.30    0.30    --  111.00 -77.00 -30.00   85
 48  \w    103.00 129.10   0.30    0.30    --  111.00  38.00 150.00   87
 49  \w     63.00  88.80   0.30    0.30    --  111.00 -50.00-150.00   86
 50  \w    147.00 173.10   0.30    0.30    --  111.00 111.00   0.00   87
 51  \w    135.00 175.20   0.30    0.30    --  111.00  50.00-120.00  134
 52  \w     94.00 142.00   0.30    0.30    --  111.00  50.00  30.00  160
 53  \w     82.00 107.80   0.30    0.30    --  111.00 -77.00  30.00   86
 54  \w    111.00 142.20   0.30    0.30    --  111.00  25.00 -90.00  104
 55  \w    115.00 144.10   0.30    0.30    --  111.00 178.00 -60.00   97
 56  \w     84.00 150.00   0.30    0.30    --  111.00 178.00  30.00  220
 57  \w     51.00  76.80   0.30    0.30    --  111.00  -5.00  54.09   86
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0478993000
_diffrn_orient_matrix_UB_12      0.0006927000
_diffrn_orient_matrix_UB_13      -0.1748853000
_diffrn_orient_matrix_UB_21      -0.0521582000
_diffrn_orient_matrix_UB_22      0.0299310000
_diffrn_orient_matrix_UB_23      -0.0122324000
_diffrn_orient_matrix_UB_31      0.2434984000
_diffrn_orient_matrix_UB_32      0.0062764000
_diffrn_orient_matrix_UB_33      0.0776243000
_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  0.0404
_diffrn_reflns_av_sigmaI/netI    0.0441
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       62
_diffrn_reflns_limit_k_min       -62
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            51532
_diffrn_reflns_theta_full        74.3338
_diffrn_reflns_theta_max         73.8840
_diffrn_reflns_theta_min         2.6320
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.043
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.42099
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.316
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1056
_exptl_crystal_size_max          0.525
_exptl_crystal_size_mid          0.191
_exptl_crystal_size_min          0.130
_refine_diff_density_max         0.544
_refine_diff_density_min         -0.957
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     355
_refine_ls_number_reflns         5129
_refine_ls_number_restraints     111
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0528
_refine_ls_R_factor_gt           0.0505
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0650P)^2^+2.0855P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1272
_refine_ls_wR_factor_ref         0.1292
_reflns_number_gt                4820
_reflns_number_total             5129
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo7b00340_si_002.cif
_cod_data_source_block           ban16_pc49sn
_cod_database_code               4032454
_publcif_datablock.id            {0459ec2e-346b-42ac-b711-3200f2a81e13}