Construction of the [6,5,7,5] Tetracyclic Core of Calyciphylline A Type Alkaloids via a Tandem Semipinacol Rearrangement/Nicholas Reaction.
Shao, Hui; Bao, Wen; Jing, Ze-Ran; Wang, Yun-Peng; Zhang, Fu-Min; Wang, Shao-Hua; Tu, Yong-Qiang; Organic letters 19 (2017) 4648–4651; doi:10.1021/acs.orglett.7b02274

data_1547035
_publ_section_title
;
 Construction of the [6,5,7,5] Tetracyclic Core of Calyciphylline A Type
 Alkaloids via a Tandem Semipinacol Rearrangement/Nicholas Reaction.
;
_journal_issue                   17
_journal_name_full               'Organic letters'
_journal_page_first              4648
_journal_page_last               4651
_journal_paper_doi               10.1021/acs.orglett.7b02274
_journal_volume                  19
_journal_year                    2017
_chemical_formula_moiety         'C16 H22 O4'
_chemical_formula_sum            'C16 H22 O4'
_chemical_formula_weight         278.33
_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     direct
_audit_creation_date             2017-05-10
_audit_creation_method
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Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
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_cell_angle_alpha                90
_cell_angle_beta                 114.177(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.7343(9)
_cell_length_b                   13.3055(8)
_cell_length_c                   11.7856(11)
_cell_measurement_reflns_used    715
_cell_measurement_temperature    292.53(10)
_cell_measurement_theta_max      23.9640
_cell_measurement_theta_min      3.6980
_cell_volume                     1535.6(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
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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, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      292.53(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega   58.00   92.50   1.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867   57.0000  -60.0000 23

  2 omega  -18.00   67.50   1.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867  -99.0000  -90.0000 57

  3 omega   -1.00   92.00   1.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867   77.0000   30.0000 62
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0474466000
_diffrn_orient_matrix_UB_12      -0.0369906000
_diffrn_orient_matrix_UB_13      0.0003211000
_diffrn_orient_matrix_UB_21      -0.0486755000
_diffrn_orient_matrix_UB_22      0.0381477000
_diffrn_orient_matrix_UB_23      -0.0067445000
_diffrn_orient_matrix_UB_31      -0.0250367000
_diffrn_orient_matrix_UB_32      -0.0040734000
_diffrn_orient_matrix_UB_33      -0.0656289000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0425
_diffrn_reflns_av_unetI/netI     0.0910
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            5425
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.020
_diffrn_reflns_theta_min         3.339
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.085
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49103
_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
;
;
_exptl_crystal_density_diffrn    1.204
_exptl_crystal_description
;
;
_exptl_crystal_F_000             600
_refine_diff_density_max         0.170
_refine_diff_density_min         -0.176
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.003
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     192
_refine_ls_number_reflns         3024
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.003
_refine_ls_R_factor_all          0.1323
_refine_ls_R_factor_gt           0.0616
_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^)+(0.0507P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1209
_refine_ls_wR_factor_ref         0.1612
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1540
_reflns_number_total             3024
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b02274_si_004.cif
_cod_data_source_block           shaoh_0508_2
_cod_database_code               1547035
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H O N'
_reflns_odcompleteness_completeness 99.70
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Fixed Sof: H8AA(0.65) H8AB(0.65) H8BC(0.35) H8BD(0.35) H10A(0.65) H10B(0.65)
 H10C(0.35) H10D(0.35) C9(0.65) H9A(0.65) H9B(0.65) C9'(0.35) H9'A(0.35)
 H9'B(0.35)
3.a Ternary CH refined with riding coordinates:
 C5(H5)
3.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C8(H8AA,H8AB), C8(H8BC,H8BD), C10(H10A,H10B),
 C10(H10C,H10D), C11(H11A,H11B), C15(H15A,H15B), C9(H9A,H9B), C9'(H9'A,H9'B)
3.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C16(H16A,H16B,H16C)
3.d :
 C13(H13)
;
_olex2_date_sample_data_collection 2017-05-09
_olex2_submission_special_instructions 'No special instructions were received'