Total Synthesis of (±)-Lycojaponicumin D and Lycodoline-Type Lycopodium Alkaloids.
Zhao, Xian-He; Zhang, Qing; Du, Ji-Yuan; Lu, Xin-Yun; Cao, Ye-Xing; Deng, Yu-Hua; Fan, Chun-An; Journal of the American Chemical Society 139 (2017) 7095–7103; doi:10.1021/jacs.7b03280

data_4126136
_publ_section_title
;
 Total Synthesis of (+-)-Lycojaponicumin D and Lycodoline-Type Lycopodium
 Alkaloids.
;
_journal_issue                   20
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              7095
_journal_page_last               7103
_journal_paper_doi               10.1021/jacs.7b03280
_journal_volume                  139
_journal_year                    2017
_chemical_formula_moiety         'C16 H27 N O3'
_chemical_formula_sum            'C16 H27 N O3'
_chemical_formula_weight         281.39
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-03-20
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 106.701(7)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   12.4770(9)
_cell_length_b                   8.3561(3)
_cell_length_c                   15.4163(8)
_cell_measurement_reflns_used    1681
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      26.1830
_cell_measurement_theta_min      4.1910
_cell_volume                     1539.49(16)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
  1 omega   49.00   76.00   1.5000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854  178.0000  -30.0000 18

  2 omega   69.00   96.00   1.5000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854  178.0000 -180.0000 18

  3 omega  -17.00   82.00   1.5000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854   19.0000 -180.0000 66

  4 omega  -35.00   40.00   1.5000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854  -57.0000  -30.0000 50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0318208000
_diffrn_orient_matrix_UB_12      -0.0060236000
_diffrn_orient_matrix_UB_13      -0.0460890000
_diffrn_orient_matrix_UB_21      -0.0221671000
_diffrn_orient_matrix_UB_22      -0.0741967000
_diffrn_orient_matrix_UB_23      0.0091783000
_diffrn_orient_matrix_UB_31      -0.0449611000
_diffrn_orient_matrix_UB_32      0.0407763000
_diffrn_orient_matrix_UB_33      0.0098596000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0284
_diffrn_reflns_av_unetI/netI     0.0471
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            6004
_diffrn_reflns_theta_full        25.50
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         3.41
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.083
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69106
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
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            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.214
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             616
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.34
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.168
_refine_diff_density_min         -0.181
_refine_diff_density_rms         0.037
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     184
_refine_ls_number_reflns         3035
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0821
_refine_ls_R_factor_gt           0.0524
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0473P)^2^+0.1421P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1105
_refine_ls_wR_factor_ref         0.1288
_reflns_number_gt                2026
_reflns_number_total             3035
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja7b03280_si_004.cif
_cod_data_source_block           zhaoxh0305
_cod_original_cell_volume        1539.48(15)
_cod_database_code               4126136
_reflns_odcompleteness_completeness 99.70
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Others
 Fixed Uiso: H2(0.073) H3(0.094) H2A(0.046) H2B(0.046) H3A(0.059) H4A(0.07)
 H4B(0.07) H5(0.061) H7A(0.065) H7B(0.065) H8A(0.071) H8B(0.071) H9A(0.062)
 H9B(0.062) H10A(0.053) H10B(0.053) H12A(0.071) H12B(0.071) H13A(0.109)
 H13B(0.109) H13C(0.109) H14A(0.052) H14B(0.052) H15A(0.063) H15B(0.063)
 H16A(0.071) H16B(0.071)
 Fixed X: H2(0.3244) H3(0.18) H2A(0.4364) H2B(0.3937) H3A(0.5956) H4A(0.5295)
 H4B(0.6334) H5(0.4847) H7A(0.3125) H7B(0.2861) H8A(0.12) H8B(0.1418)
 H9A(0.1933) H9B(0.0968) H10A(0.3695) H10B(0.4375) H12A(0.6163) H12B(0.5008)
 H13A(0.6092) H13B(0.6809) H13C(0.563) H14A(0.2289) H14B(0.3073) H15A(0.1349)
 H15B(0.0724) H16A(0.2252) H16B(0.0953)
 Fixed Y: H2(0.7725) H3(1.0519) H2A(1.0539) H2B(1.0446) H3A(0.9154)
 H4A(0.8729) H4B(0.7949) H5(0.6107) H7A(0.5166) H7B(0.5227) H8A(0.5531)
 H8B(0.7065) H9A(0.6782) H9B(0.7846) H10A(0.668) H10B(0.8219) H12A(0.5599)
 H12B(0.4759) H13A(1.1846) H13B(1.0877) H13C(1.1536) H14A(0.908) H14B(1.0383)
 H15A(1.1505) H15B(1.0331) H16A(1.2651) H16B(1.2919)
 Fixed Z: H2(0.2832) H3(0.1107) H2A(0.0845) H2B(0.1705) H3A(0.1539)
 H4A(0.3123) H4B(0.2913) H5(0.2791) H7A(0.1093) H7B(0.203) H8A(0.0834)
 H8B(0.145) H9A(-0.0211) H9B(-0.0059) H10A(-0.0012) H10B(-0.0081) H12A(0.1973)
 H12B(0.155) H13A(0.1907) H13B(0.2744) H13C(0.2736) H14A(-0.0863) H14B(-0.0271)
 H15A(-0.1083) H15B(-0.0599) H16A(0.0341) H16B(0.0046)
;
_olex2_date_sample_data_collection 2015-03-04
_olex2_submission_special_instructions 'No special instructions were received'