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_1546237
_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_absolute_configuration unk
_chemical_formula_moiety         'C28 H25 N O4'
_chemical_formula_sum            'C28 H25 N O4'
_chemical_formula_weight         439.49
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_symmetry_space_group_name_Hall  'P 2c -2ac'
_symmetry_space_group_name_H-M   'P c a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-05-28
_audit_creation_method
;
Olex2 1.2
(compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   14.8441(2)
_cell_length_b                   10.42006(18)
_cell_length_c                   14.7439(3)
_cell_measurement_reflns_used    4641
_cell_measurement_temperature    294.40(10)
_cell_measurement_theta_max      70.7820
_cell_measurement_theta_min      4.1950
_cell_volume                     2280.53(7)
_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    'olex2.solve (Bourhis et al., 2013)'
_diffrn_ambient_temperature      294.40(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0579835000
_diffrn_orient_matrix_UB_12      -0.0922112000
_diffrn_orient_matrix_UB_13      -0.0571593000
_diffrn_orient_matrix_UB_21      0.0685519000
_diffrn_orient_matrix_UB_22      -0.0095436000
_diffrn_orient_matrix_UB_23      0.0781150000
_diffrn_orient_matrix_UB_31      -0.0520150000
_diffrn_orient_matrix_UB_32      -0.1152129000
_diffrn_orient_matrix_UB_33      0.0393405000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0288
_diffrn_reflns_av_unetI/netI     0.0287
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            7959
_diffrn_reflns_theta_full        70.54
_diffrn_reflns_theta_max         70.54
_diffrn_reflns_theta_min         5.96
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.688
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77354
_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    1.280
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             928
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.33
_refine_diff_density_max         0.171
_refine_diff_density_min         -0.192
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.0(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     300
_refine_ls_number_reflns         3174
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0417
_refine_ls_R_factor_gt           0.0404
_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^)+(0.0757P)^2^+0.0395P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1066
_refine_ls_wR_factor_ref         0.1089
_reflns_number_gt                3066
_reflns_number_total             3174
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ol7b01202_si_004.cif
_cod_data_source_block           anxt0517
_cod_original_cell_volume        2280.54(7)
_cod_database_code               1546237
_reflns_odcompleteness_completeness 99.36
_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:
 C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B), C9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 C19(H19), C16(H16), C24(H24), C26(H26), C27(H27), C10(H10), C3(H3), C6(H6),
 C25(H25), C17(H17), C5(H5), C28(H28), C20(H20), C4(H4)
2.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C21(H21A,H21B,H21C)
;