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_1555689
_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         'C13 H19 N O2'
_chemical_formula_sum            'C13 H19 N O2'
_chemical_formula_weight         221.29
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-04-15
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 98.254(9)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   7.6484(7)
_cell_length_b                   7.0465(6)
_cell_length_c                   10.9071(9)
_cell_measurement_reflns_used    871
_cell_measurement_temperature    293.42(10)
_cell_measurement_theta_max      28.4850
_cell_measurement_theta_min      4.2060
_cell_volume                     581.74(9)
_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      293.42(10)
_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   -6.00   24.00   2.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -17.3041  -99.0000  150.0000 15

  2 omega  -19.00   83.00   2.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       20.7416    0.0000  -90.0000 51

  3 omega  -23.00   53.00   2.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       20.7416   19.0000    0.0000 38
;
_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      0.0128415000
_diffrn_orient_matrix_UB_12      -0.0550005000
_diffrn_orient_matrix_UB_13      0.0550134000
_diffrn_orient_matrix_UB_21      0.0928352000
_diffrn_orient_matrix_UB_22      0.0068502000
_diffrn_orient_matrix_UB_23      0.0015228000
_diffrn_orient_matrix_UB_31      0.0008722000
_diffrn_orient_matrix_UB_32      0.0840514000
_diffrn_orient_matrix_UB_33      0.0358492000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0222
_diffrn_reflns_av_unetI/netI     0.0417
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            2152
_diffrn_reflns_theta_full        25.50
_diffrn_reflns_theta_max         26.01
_diffrn_reflns_theta_min         3.45
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.085
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81188
_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.
;
_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    1.263
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             240
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.31
_exptl_crystal_size_min          0.28
_refine_diff_density_max         0.149
_refine_diff_density_min         -0.182
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.2(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.099
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     146
_refine_ls_number_reflns         1730
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.098
_refine_ls_R_factor_all          0.0469
_refine_ls_R_factor_gt           0.0417
_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^)+(0.0425P)^2^+0.0640P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0952
_refine_ls_wR_factor_ref         0.0995
_reflns_number_gt                1569
_reflns_number_total             1730
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ol6b02072_si_001.cif
_cod_data_source_block           madh0410
_cod_original_cell_volume        581.75(9)
_cod_database_code               1555689
_reflns_odcompleteness_completeness 99.61
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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.a Ternary CH refined with riding coordinates:
 C4(H4), C9(H9), 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)
2.c Aromatic/amide H refined with riding coordinates:
 N1(H1)
2.d Idealised Me refined as rotating group:
 C13(H13a,H13b,H13c)
;
_olex2_date_sample_data_collection 2015-04-14
_olex2_submission_special_instructions 'No special instructions were received'