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_1546075
_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         'C19 H21 N O5'
_chemical_formula_sum            'C19 H21 N O5'
_chemical_formula_weight         343.36
_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     direct
_audit_creation_date             2014-03-05
_audit_creation_method
;
Olex2 1.2
(compiled 2014.02.28 svn.r2899 for OlexSys, GUI svn.r4781)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.133(12)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   8.4092(11)
_cell_length_b                   18.977(2)
_cell_length_c                   21.008(3)
_cell_measurement_reflns_used    1133
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      19.6980
_cell_measurement_theta_min      3.3630
_cell_volume                     3350.2(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
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
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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 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0738813000
_diffrn_orient_matrix_UB_12      0.0060256000
_diffrn_orient_matrix_UB_13      -0.0143091000
_diffrn_orient_matrix_UB_21      0.0197192000
_diffrn_orient_matrix_UB_22      -0.0361387000
_diffrn_orient_matrix_UB_23      0.0038466000
_diffrn_orient_matrix_UB_31      -0.0356653000
_diffrn_orient_matrix_UB_32      -0.0074632000
_diffrn_orient_matrix_UB_33      -0.0303622000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1024
_diffrn_reflns_av_unetI/netI     0.1493
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            15285
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.214
_diffrn_reflns_theta_max         25.994
_diffrn_reflns_theta_min         2.891
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.099
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.25120
_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_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.362
_exptl_crystal_description       block
_exptl_crystal_F_000             1456
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.231
_refine_diff_density_min         -0.194
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     453
_refine_ls_number_reflns         6578
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.2311
_refine_ls_R_factor_gt           0.0995
_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^)+(0.0918P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2197
_refine_ls_wR_factor_ref         0.2904
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2482
_reflns_number_total             6578
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b01202_si_008.cif
_cod_data_source_block           Compound_6
_cod_depositor_comments
;
Adding full bibliography for 1546073--1546077.cif.

2019-02-18
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_cell_volume        3350.2(8)
_cod_original_formula_moiety     '2(C19 H21 N O5)'
_cod_original_formula_sum        'C38 H42 N2 O10'
_cod_original_formula_units_Z    4
_cod_original_formula_weight     686.73
_cod_database_code               1546075
_shelxl_version_number           2013-2
_reflns_odcompleteness_completeness 99.56
_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:
 C27(H27), C34(H34), C9(H9), C15(H15)
2.b Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B), C32(H32A,
 H32B), C33(H33A,H33B), C35(H35A,H35B), C2(H2A,H2B), C11(H11A,H11B), C12(H12A,
 H12B), C13(H13A,H13B), C14(H14A,H14B), C16(H16A,H16B), C44(H44A,H44B)
2.c Aromatic/amide H refined with riding coordinates:
 C22(H22), C25(H25), C4(H4), C7(H7)
2.d Idealised Me refined as rotating group:
 C37(H37A,H37B,H37C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              1981
_shelx_hkl_checksum              59130
_olex2_computing_structure_refinement_long 'ShelXL (Sheldrick, 2008)'
_olex2_computing_structure_solution_long 'ShelXS (Sheldrick, 2008)'