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_1555688
_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     iterative
_audit_creation_date             2015-07-08
_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            8
_cell_length_a                   10.9468(4)
_cell_length_b                   13.1316(5)
_cell_length_c                   19.8805(8)
_cell_measurement_reflns_used    3339
_cell_measurement_temperature    296.71(10)
_cell_measurement_theta_max      69.7990
_cell_measurement_theta_min      4.0680
_cell_volume                     2857.80(19)
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      296.71(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_details
;
  1 omega   29.00   60.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   38.0000  -90.0000 31

  2 omega   35.00   72.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -57.0000  -60.0000 37

  3 omega   37.00   63.00   1.0000    3.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000 -150.0000 26

  4 omega   45.00   90.00   1.0000    3.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -50.0000 -180.0000 45

  5 omega   87.00  149.00   1.0000    3.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   25.0000 -120.0000 62

  6 omega   40.00   66.00   1.0000    3.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000    0.0000 26

  7 omega   36.00   92.00   1.0000    3.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000   30.0000 56

  8 omega   62.00   89.00   1.0000    3.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000  120.0000 27

  9 omega   36.00   91.00   1.0000    3.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000   90.0000 55

 10 omega   42.00   92.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   58.0000  150.0000 50

 11 omega    3.00   75.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -38.0000  150.0000 72

 12 omega  -14.00   14.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -57.0000   60.0000 28

 13 omega  -69.00   -4.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000  -30.0000 65
;
_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      0.0162006000
_diffrn_orient_matrix_UB_12      -0.0514659000
_diffrn_orient_matrix_UB_13      -0.0690177000
_diffrn_orient_matrix_UB_21      0.0972767000
_diffrn_orient_matrix_UB_22      -0.0714437000
_diffrn_orient_matrix_UB_23      0.0301776000
_diffrn_orient_matrix_UB_31      -0.1003473000
_diffrn_orient_matrix_UB_32      -0.0776882000
_diffrn_orient_matrix_UB_33      0.0179644000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0155
_diffrn_reflns_av_unetI/netI     0.0284
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            6759
_diffrn_reflns_point_group_measured_fraction_full 0.930
_diffrn_reflns_point_group_measured_fraction_max 0.841
_diffrn_reflns_theta_full        25.500
_diffrn_reflns_theta_max         69.974
_diffrn_reflns_theta_min         4.035
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.626
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84572
_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    1.215
_exptl_crystal_description       block
_exptl_crystal_F_000             1136
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.33
_refine_diff_density_max         0.144
_refine_diff_density_min         -0.136
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 1322 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.05(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     345
_refine_ls_number_reflns         4552
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0442
_refine_ls_R_factor_gt           0.0395
_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^)+(0.0496P)^2^+0.2605P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0987
_refine_ls_wR_factor_ref         0.1037
_reflns_Friedel_coverage         0.519
_reflns_Friedel_fraction_full    0.818
_reflns_Friedel_fraction_max     0.659
_reflns_number_gt                4128
_reflns_number_total             4552
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol6b02072_si_003.cif
_cod_data_source_block           mdh_0707
_cod_database_code               1555688
_reflns_odcompleteness_completeness 99.55
_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:
 C2(H2), C10(H10), C11(H11), C15(H15), C19(H19), C27(H27), C28(H28), C32(H32)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C8(H8A,H8B), C9(H9A,H9B), C12(H12A,
 H12B), C14(H14A,H14B), C16(H16A,H16B), C20(H20A,H20B), C21(H21A,H21B),
 C22(H22A,H22B), C25(H25A,H25B), C26(H26A,H26B), C29(H29A,H29B), C31(H31A,H31B),
  C33(H33A,H33B)
2.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C34(H34A,H34B,H34C)
;
_shelx_res_checksum              14535
_shelx_hkl_checksum              60182
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'