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_1546073
_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 H23 N O6'
_chemical_formula_sum            'C24 H23 N O6'
_chemical_formula_weight         421.43
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 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                 95.091(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.6711(6)
_cell_length_b                   19.4443(14)
_cell_length_c                   11.2024(7)
_cell_measurement_reflns_used    887
_cell_measurement_temperature    292.13(10)
_cell_measurement_theta_max      20.2480
_cell_measurement_theta_min      3.7860
_cell_volume                     2098.3(2)
_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      292.13(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.9964
_diffrn_measured_fraction_theta_max 0.8789
_diffrn_measurement_details
;
  1 omega -103.00  -63.40   1.2000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.2137  178.0000 -120.0000 33

  2 omega -103.00  -76.60   1.2000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.2137  178.0000  -30.0000 22

  3 omega  -52.00   62.00   1.2000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512  -19.0000  -60.0000 95

  4 omega  -32.00   37.60   1.2000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512  -57.0000 -150.0000 58
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0232005000
_diffrn_orient_matrix_UB_12      -0.0300934000
_diffrn_orient_matrix_UB_13      0.0313845000
_diffrn_orient_matrix_UB_21      0.0576687000
_diffrn_orient_matrix_UB_22      0.0184932000
_diffrn_orient_matrix_UB_23      0.0274188000
_diffrn_orient_matrix_UB_31      -0.0395441000
_diffrn_orient_matrix_UB_32      0.0091773000
_diffrn_orient_matrix_UB_33      0.0479173000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0762
_diffrn_reflns_av_unetI/netI     0.1513
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            8435
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.500
_diffrn_reflns_theta_max         26.019
_diffrn_reflns_theta_min         3.096
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.096
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.98975
_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    1.334
_exptl_crystal_description       block
_exptl_crystal_F_000             888
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.278
_refine_diff_density_min         -0.221
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.001
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     282
_refine_ls_number_reflns         4114
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.001
_refine_ls_R_factor_all          0.2040
_refine_ls_R_factor_gt           0.0758
_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^)+(0.0478P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1386
_refine_ls_wR_factor_ref         0.1956
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1648
_reflns_number_total             4114
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b01202_si_007.cif
_cod_data_source_block           maxy0617_2
_cod_depositor_comments
'Adding full bibliography for 1546073--1546077.cif.'
_cod_database_code               1546073
_reflns_odcompleteness_completeness 99.64
_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.a Ternary CH refined with riding coordinates:
 C5(H5)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C6(H6A,H6B), C7(H7A,H7B), C13(H13A,H13B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C10(H10), C11(H11), C15(H15), C19(H19), C20(H20), C22(H22), C23(H23)
2.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C24(H24A,H24B,H24C)
;
_shelx_hkl_checksum              29364
_shelx_res_checksum              22598
_shelxl_version_number           2013-2