Protecting-Group-Free Total Synthesis of (-)-Lycopodine via Phosphoric Acid Promoted Alkyne Aza-Prins Cyclization.
Ma, Donghui; Zhong, Zhuliang; Liu, Zaimin; Zhang, Mingjie; Xu, Shiyan; Xu, Dengyu; Song, Dengpeng; Xie, Xingang; She, Xuegong; Organic letters 18 (2016) 4328–4331; doi:10.1021/acs.orglett.6b02072

data_1555687
_publ_section_title
;
 Protecting-Group-Free Total Synthesis of (-)-Lycopodine via Phosphoric
 Acid Promoted Alkyne Aza-Prins Cyclization.
;
_journal_issue                   17
_journal_name_full               'Organic letters'
_journal_page_first              4328
_journal_page_last               4331
_journal_paper_doi               10.1021/acs.orglett.6b02072
_journal_volume                  18
_journal_year                    2016
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C16 H23 N O2'
_chemical_formula_sum            'C16 H23 N O2'
_chemical_formula_weight         261.35
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-06-11
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.48040(11)
_cell_length_b                   10.49020(19)
_cell_length_c                   18.4048(3)
_cell_measurement_reflns_used    2637
_cell_measurement_temperature    294.1(5)
_cell_measurement_theta_max      69.6920
_cell_measurement_theta_min      10.5250
_cell_volume                     1444.24(4)
_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_environment      air
_diffrn_ambient_temperature      294.1(5)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.951
_diffrn_measured_fraction_theta_max 0.939
_diffrn_measurement_details
;
  1 omega  -14.00   68.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -57.0000   30.0000 82

  2 omega   78.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000 -125.0000  -30.0000 26

  3 omega   71.00  113.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000 -150.0000 42

  4 omega   47.00   91.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -25.0000 -150.0000 44

  5 omega   40.00   90.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000 -150.0000 50

  6 omega   43.00   83.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000  -90.0000 40

  7 omega   40.00   69.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000 -180.0000 29

  8 omega   34.00  121.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   57.0000  -90.0000 87

  9 omega   98.00  123.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   57.0000    0.0000 25

 10 omega   39.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -50.0000   60.0000 65

 11 omega   65.00   98.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  150.0000 33

 12 omega   43.00  119.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -63.0000  150.0000 76
;
_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      0.1418611000
_diffrn_orient_matrix_UB_12      0.1064679000
_diffrn_orient_matrix_UB_13      -0.0035431000
_diffrn_orient_matrix_UB_21      -0.1445391000
_diffrn_orient_matrix_UB_22      0.0999506000
_diffrn_orient_matrix_UB_23      0.0174927000
_diffrn_orient_matrix_UB_31      0.0371514000
_diffrn_orient_matrix_UB_32      -0.0167475000
_diffrn_orient_matrix_UB_33      0.0817198000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0167
_diffrn_reflns_av_unetI/netI     0.0196
_diffrn_reflns_Laue_measured_fraction_full 0.951
_diffrn_reflns_Laue_measured_fraction_max 0.939
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            4026
_diffrn_reflns_point_group_measured_fraction_full 0.906
_diffrn_reflns_point_group_measured_fraction_max 0.885
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.742
_diffrn_reflns_theta_min         10.542
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.619
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76866
_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_density_diffrn    1.202
_exptl_crystal_description       block
_exptl_crystal_F_000             568
_exptl_crystal_size_max          0.41
_exptl_crystal_size_mid          0.37
_exptl_crystal_size_min          0.35
_refine_diff_density_max         0.300
_refine_diff_density_min         -0.343
_refine_diff_density_rms         0.122
_refine_ls_abs_structure_details
;
 Flack x determined using 875 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.1(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.107
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     173
_refine_ls_number_reflns         2416
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.107
_refine_ls_R_factor_all          0.0522
_refine_ls_R_factor_gt           0.0513
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0851P)^2^+0.1068P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1299
_refine_ls_wR_factor_ref         0.1317
_reflns_Friedel_coverage         0.617
_reflns_Friedel_fraction_full    0.841
_reflns_Friedel_fraction_max     0.810
_reflns_number_gt                2346
_reflns_number_total             2416
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol6b02072_si_002.cif
_cod_data_source_block           mdh0608
_cod_database_code               1555687
_reflns_odcompleteness_completeness 94.83
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C4(H4), C5(H5), C11(H11)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C6(H6A,H6B), C8(H8A,H8B), C10(H10A,H10B), C12(H12A,
 H12B), C14(H14A,H14B)
2.c Aromatic/amide H refined with riding coordinates:
 C15(H15)
2.d X=CH2 refined with riding coordinates:
 C16(H16A,H16B)
2.e Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'