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_1546077
_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 H22 Br N O5'
_chemical_formula_sum            'C24 H22 Br N O5'
_chemical_formula_weight         484.33
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2013-06-20
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.857(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.1412(16)
_cell_length_b                   18.601(4)
_cell_length_c                   11.3292(16)
_cell_measurement_reflns_used    1485
_cell_measurement_temperature    292.11(10)
_cell_measurement_theta_max      22.1370
_cell_measurement_theta_min      3.7420
_cell_volume                     2136.0(6)
_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
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution    'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      292.11(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.9774
_diffrn_measured_fraction_theta_max 0.8666
_diffrn_measurement_details
;
  1 omega   -1.00   90.50   1.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512   57.0000  120.0000 61

  2 omega  -10.00   17.00   1.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512   77.0000 -150.0000 18

  3 omega   63.00   94.50   1.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512   77.0000 -150.0000 21

  4 omega  -48.00   45.00   1.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512  -57.0000  -30.0000 62
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0669063000
_diffrn_orient_matrix_UB_12      -0.0112138000
_diffrn_orient_matrix_UB_13      0.0004022000
_diffrn_orient_matrix_UB_21      -0.0202812000
_diffrn_orient_matrix_UB_22      -0.0354188000
_diffrn_orient_matrix_UB_23      -0.0151691000
_diffrn_orient_matrix_UB_31      0.0031088000
_diffrn_orient_matrix_UB_32      0.0086724000
_diffrn_orient_matrix_UB_33      -0.0607432000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0813
_diffrn_reflns_av_unetI/netI     0.1499
_diffrn_reflns_Laue_measured_fraction_full 0.974
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            8241
_diffrn_reflns_point_group_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        25.500
_diffrn_reflns_theta_max         26.022
_diffrn_reflns_theta_min         2.951
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.961
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.30567
_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 yellow'
_exptl_crystal_density_diffrn    1.506
_exptl_crystal_description       block
_exptl_crystal_F_000             992
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.750
_refine_diff_density_min         -0.889
_refine_diff_density_rms         0.116
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.005
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     281
_refine_ls_number_reflns         4095
_refine_ls_number_restraints     42
_refine_ls_restrained_S_all      1.008
_refine_ls_R_factor_all          0.1809
_refine_ls_R_factor_gt           0.0773
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.1101P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1765
_refine_ls_wR_factor_ref         0.2735
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1745
_reflns_number_total             4095
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b01202_si_006.cif
_cod_data_source_block           maxy0617
_cod_depositor_comments
'Adding full bibliography for 1546073--1546077.cif.'
_cod_database_code               1546077
_reflns_odcompleteness_completeness 97.74
_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 C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C18) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C22) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3.a Ternary CH refined with riding coordinates:
 C1(H1)
3.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C6(H6A,H6B), C7(H7A,H7B), C12(H12A,H12B), C18(H18A,H18B)
3.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C10(H10), C14(H14), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23)
3.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C)
;
_shelx_hkl_checksum              90791
_shelx_res_checksum              87285
_shelxl_version_number           2013-2