Au-Catalyzed [2 + 3] Annulation of Enamides with Propargyl Esters: Total Synthesis of Cephalotaxine and Cephalezomine H.
Ma, Xiao-Yan; An, Xian-Tao; Zhao, Xian-He; Du, Ji-Yuan; Deng, Yu-Hua; Zhang, Xiang-Zhi; Fan, Chun-An; Organic letters 19 (2017) 2965–2968; doi:10.1021/acs.orglett.7b01202

data_1546238
_publ_section_title
;
 Au-Catalyzed [2 + 3] Annulation of Enamides with Propargyl Esters: Total
 Synthesis of Cephalotaxine and Cephalezomine H.
;
_journal_issue                   11
_journal_name_full               'Organic letters'
_journal_page_first              2965
_journal_page_last               2968
_journal_paper_doi               10.1021/acs.orglett.7b01202
_journal_volume                  19
_journal_year                    2017
_chemical_formula_moiety         'C17 H19 N O5'
_chemical_formula_sum            'C17 H19 N O5'
_chemical_formula_weight         317.33
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-09-22
_audit_creation_method
;
Olex2 1.2
(compiled 2014.08.28 svn.r2986 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                70.672(6)
_cell_angle_beta                 84.194(7)
_cell_angle_gamma                80.842(5)
_cell_formula_units_Z            2
_cell_length_a                   8.1791(6)
_cell_length_b                   8.4632(4)
_cell_length_c                   11.3125(9)
_cell_measurement_reflns_used    1946
_cell_measurement_temperature    292.5(2)
_cell_measurement_theta_max      28.2950
_cell_measurement_theta_min      3.8380
_cell_volume                     728.52(9)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_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      292.5(2)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
  1 omega  -46.00  -21.00   1.0000    1.2000
omega____ theta____ kappa____ phi______ frames
    -      -16.5133   77.0000   90.0000 25

  2 omega   66.00   96.00   1.0000    1.2000
omega____ theta____ kappa____ phi______ frames
    -       19.9508  178.0000 -150.0000 30

  3 omega  -20.00   59.00   1.0000    1.2000
omega____ theta____ kappa____ phi______ frames
    -       19.9508  -99.0000 -120.0000 79

  4 omega  -21.00   41.00   1.0000    1.2000
omega____ theta____ kappa____ phi______ frames
    -       19.9508  -38.0000  -30.0000 62

  5 omega  -47.00   83.00   1.0000    1.2000
omega____ theta____ kappa____ phi______ frames
    -       19.9508    0.0000 -150.0000 130

  6 omega  -10.00   34.00   1.0000    1.2000
omega____ theta____ kappa____ phi______ frames
    -       19.9508   77.0000    0.0000 44
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0869657000
_diffrn_orient_matrix_UB_12      -0.0195871000
_diffrn_orient_matrix_UB_13      -0.0091656000
_diffrn_orient_matrix_UB_21      -0.0107622000
_diffrn_orient_matrix_UB_22      0.0016691000
_diffrn_orient_matrix_UB_23      -0.0618554000
_diffrn_orient_matrix_UB_31      0.0076174000
_diffrn_orient_matrix_UB_32      0.0874393000
_diffrn_orient_matrix_UB_33      -0.0227347000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0203
_diffrn_reflns_av_unetI/netI     0.0409
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            5040
_diffrn_reflns_theta_full        25.50
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         3.36
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.107
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80656
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.447
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             336
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.34
_exptl_crystal_size_min          0.29
_refine_diff_density_max         0.214
_refine_diff_density_min         -0.198
_refine_diff_density_rms         0.043
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     210
_refine_ls_number_reflns         2865
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0626
_refine_ls_R_factor_gt           0.0462
_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^)+(0.0426P)^2^+0.2462P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1030
_refine_ls_wR_factor_ref         0.1147
_reflns_number_gt                2230
_reflns_number_total             2865
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ol7b01202_si_010.cif
_cod_data_source_block           maxy0922
_cod_original_cell_volume        728.53(9)
_cod_database_code               1546238
_reflns_odcompleteness_completeness 99.66
_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
 At 1.5 times of:
  All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C10(H10), C15(H15), C16(H16)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C6(H6A,H6B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B),
 C17(H17A,H17B)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4A), C8(H8)
2.d Idealised tetrahedral OH refined as rotating group:
 O4(H4), O5(H5)
;
_olex2_submission_special_instructions 'No special instructions were received'