Phosphine-Catalyzed Asymmetric (3 + 2) Annulations of δ-Acetoxy Allenoates with β-Carbonyl Amides: Enantioselective Synthesis of Spirocyclic β-Keto γ-Lactams.
Ni, Chunjie; Chen, Jiangfei; Zhang, Yuwen; Hou, Yading; Wang, Dong; Tong, Xiaofeng; Zhu, Shou-Fei; Zhou, Qi-Lin; Organic letters 19 (2017) 3668–3671; doi:10.1021/acs.orglett.7b01717

data_1546419
_publ_section_title
;
 Phosphine-Catalyzed Asymmetric (3 + 2) Annulations of \d-Acetoxy
 Allenoates with \b-Carbonyl Amides: Enantioselective Synthesis of
 Spirocyclic \b-Keto \g-Lactams.
;
_journal_issue                   13
_journal_name_full               'Organic letters'
_journal_page_first              3668
_journal_page_last               3671
_journal_paper_doi               10.1021/acs.orglett.7b01717
_journal_volume                  19
_journal_year                    2017
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C34 H34 Br N O5'
_chemical_formula_sum            'C34 H34 Br N O5'
_chemical_formula_weight         616.53
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2016-11-25
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5261)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.276(8)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.428(4)
_cell_length_b                   5.8759(18)
_cell_length_c                   21.526(6)
_cell_measurement_reflns_used    1278
_cell_measurement_temperature    296
_cell_measurement_theta_max      19.373
_cell_measurement_theta_min      2.325
_cell_volume                     1551.4(8)
_computing_cell_refinement       'SAINT V7.66A (?, 2016)'
_computing_data_reduction        'SAINT V7.66A (?, 2016)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.874
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0683
_diffrn_reflns_av_unetI/netI     0.1535
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.874
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            10848
_diffrn_reflns_point_group_measured_fraction_full 0.865
_diffrn_reflns_point_group_measured_fraction_max 0.708
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.291
_diffrn_reflns_theta_min         1.660
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.366
_exptl_absorpt_correction_T_max  0.7460
_exptl_absorpt_correction_T_min  0.5066
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0970 before and 0.0624 after correction.
The Ratio of minimum to maximum transmission is 0.6791.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.320
_exptl_crystal_description       block
_exptl_crystal_F_000             640
_refine_diff_density_max         0.291
_refine_diff_density_min         -0.416
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Flack x determined using 638 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.028(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.894
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     372
_refine_ls_number_reflns         6600
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.894
_refine_ls_R_factor_all          0.1920
_refine_ls_R_factor_gt           0.0638
_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^)+(0.0964P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1619
_refine_ls_wR_factor_ref         0.2236
_reflns_Friedel_coverage         0.486
_reflns_Friedel_fraction_full    0.707
_reflns_Friedel_fraction_max     0.508
_reflns_number_gt                2483
_reflns_number_total             6600
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b01717_si_002.cif
_cod_data_source_block           161124
_cod_depositor_comments          'Adding full bibliography for 1546419.cif.'
_cod_database_code               1546419
_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:
 C1(H1), C2(H2)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B), C25(H25A,
 H25B), C27(H27A,H27B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C9(H9), C10(H10), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21),
 C22(H22), C23(H23), C29(H29), C30(H30), C32(H32), C33(H33)
2.d Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C34(H34A,H34B,H34C)
;
_shelx_res_checksum              9543
_shelx_hkl_checksum              13608
_shelx_shelxl_version_number     2016/6
_olex2_submission_special_instructions 'No special instructions were received'