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_1546076
_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         'C24 H25 N O5'
_chemical_formula_sum            'C24 H25 N O5'
_chemical_formula_weight         407.45
_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             2014-05-07
_audit_creation_method
;
 Olex2 1.2
 (compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816)
;
_cell_angle_alpha                80.639(4)
_cell_angle_beta                 77.851(4)
_cell_angle_gamma                78.666(4)
_cell_formula_units_Z            2
_cell_length_a                   7.5258(4)
_cell_length_b                   11.7781(5)
_cell_length_c                   12.4974(6)
_cell_measurement_reflns_used    4035
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.5210
_cell_measurement_theta_min      5.6270
_cell_volume                     1053.30(9)
_computing_cell_refinement
;
 CrysAlisPro, Agilent Technologies,
 Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
 (compiled Feb 1 2013,16:14:44)
;
_computing_data_collection
;
 CrysAlisPro, Agilent Technologies,
 Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
 (compiled Feb 1 2013,16:14:44)
;
_computing_data_reduction
;
 CrysAlisPro, Agilent Technologies,
 Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
 (compiled Feb 1 2013,16:14:44)
;
_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_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.969
_diffrn_measured_fraction_theta_max 0.969
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1289696000
_diffrn_orient_matrix_UB_12      0.1012650000
_diffrn_orient_matrix_UB_13      -0.0536727000
_diffrn_orient_matrix_UB_21      -0.1579231000
_diffrn_orient_matrix_UB_22      -0.0197160000
_diffrn_orient_matrix_UB_23      0.0981542000
_diffrn_orient_matrix_UB_31      0.0595844000
_diffrn_orient_matrix_UB_32      0.0862660000
_diffrn_orient_matrix_UB_33      0.0603629000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0227
_diffrn_reflns_av_unetI/netI     0.0283
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            7015
_diffrn_reflns_theta_full        70.60
_diffrn_reflns_theta_max         70.60
_diffrn_reflns_theta_min         3.65
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.734
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63637
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 CrysAlisPro, Agilent Technologies,
 Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
 (compiled Feb 1 2013,16:14:44)
 Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.285
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             432
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.222
_refine_diff_density_min         -0.230
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     275
_refine_ls_number_reflns         3926
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0576
_refine_ls_R_factor_gt           0.0529
_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^)+(0.0892P)^2^+0.1783P] where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1460
_refine_ls_wR_factor_ref         0.1528
_reflns_number_gt                3465
_reflns_number_total             3926
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ol7b01202_si_003.cif
_cod_data_source_block           AXT257
_cod_depositor_comments
'Adding full bibliography for 1546073--1546077.cif.'
_cod_database_code               1546076
_reflns_odcompleteness_completeness 99.22
_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)
 2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B)
 2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C19(H19), C20(H20),
 C22(H22), C23(H23)
 2.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C24(H24A,H24B,
 H24C)
;