Phosphine-Catalyzed Addition/Cycloaddition Domino Reactions of β'-Acetoxy Allenoate: Highly Stereoselective Access to 2-Oxabicyclo[3.3.1]nonane and Cyclopenta[a]pyrrolizine.
Gu, Yiting; Hu, Pengfei; Ni, Chunjie; Tong, Xiaofeng; Journal of the American Chemical Society 137 (2015) 6400–6406; doi:10.1021/jacs.5b03273

data_4123688
_publ_section_title
;
 Phosphine-Catalyzed Addition/Cycloaddition Domino Reactions of
 \b'-Acetoxy Allenoate: Highly Stereoselective Access to
 2-Oxabicyclo[3.3.1]nonane and Cyclopenta[a]pyrrolizine.
;
_journal_issue                   19
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6400
_journal_page_last               6406
_journal_paper_doi               10.1021/jacs.5b03273
_journal_volume                  137
_journal_year                    2015
_chemical_formula_moiety         'C25 H26 N2 O3'
_chemical_formula_sum            'C25 H26 N2 O3'
_chemical_formula_weight         402.48
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2015-01-21
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                102.271(2)
_cell_angle_beta                 92.338(2)
_cell_angle_gamma                90.158(2)
_cell_formula_units_Z            8
_cell_length_a                   9.5684(3)
_cell_length_b                   14.1184(5)
_cell_length_c                   33.0217(10)
_cell_measurement_reflns_used    8353
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      68.47
_cell_measurement_theta_min      3.74
_cell_volume                     4355.1(2)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXD (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.978
_diffrn_measured_fraction_theta_max 0.960
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0602
_diffrn_reflns_av_unetI/netI     0.0840
_diffrn_reflns_Laue_measured_fraction_full 0.978
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            37488
_diffrn_reflns_point_group_measured_fraction_full 0.978
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         69.792
_diffrn_reflns_theta_min         3.744
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.647
_exptl_absorpt_correction_T_max  0.7532
_exptl_absorpt_correction_T_min  0.5087
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1468 before and 0.0715 after correction.
The Ratio of minimum to maximum transmission is 0.6754.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.228
_exptl_crystal_description       plate
_exptl_crystal_F_000             1712
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.453
_refine_diff_density_min         -0.327
_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1086
_refine_ls_number_reflns         15095
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.1031
_refine_ls_R_factor_gt           0.0828
_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^)+(0.1815P)^2^+0.4901P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2363
_refine_ls_wR_factor_ref         0.2713
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11122
_reflns_number_total             15095
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b03273_si_003.cif
_cod_data_source_block           cu_dm15069_0m
_cod_depositor_comments
'Adding full bibliography for 4123688--4123689.cif.'
_cod_database_code               4123688
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.881
_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), C5B(H5B), C5A(H5A), C5C(H5C)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C10(H10A,H10B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B),
 C16(H16A,H16B), C19(H19A,H19B), C7B(H7BA,H7BB), C10B(H10C,H10D), C13B(H13C,
 H13D), C14B(H14C,H14D), C15B(H15C,H15D), C16B(H16C,H16D), C19B(H19C,H19D),
 C7A(H7AA,H7AB), C10A(H10E,H10F), C13A(H13E,H13F), C14A(H14E,H14F), C15A(H15E,
 H15F), C16A(H16E,H16F), C19A(H19E,H19F), C7C(H7CA,H7CB), C10C(H10G,H10H),
 C13C(H13G,H13H), C14C(H14G,H14H), C15C(H15G,H15H), C16C(H16G,H16H), C19C(H19G,
 H19H)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25),
 C1B(H1B), C2B(H2B), C3B(H3B), C21B(H21B), C22B(H22B), C23B(H23B), C24B(H24B),
 C25B(H25B), C1A(H1A), C2A(H2A), C3A(H3A), C21A(H21A), C22A(H22A), C23A(H23A),
 C24A(H24A), C25A(H25A), C1C(H1C), C2C(H2C), C3C(H3C), C21C(H21C), C22C(H22C),
 C23C(H23C), C24C(H24C), C25C(H25C)
2.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C17B(H17D,H17E,H17F), C17A(H17G,H17H,H17I), C17C(H17J,
 H17K,H17L)
;
_shelx_res_checksum              68726
_shelx_hkl_checksum              40067
_olex2_submission_special_instructions 'No special instructions were received'