Organocatalytic enamine-activation of cyclopropanes for highly stereoselective formation of cyclobutanes.
Halskov, Kim Søholm; Kniep, Florian; Lauridsen, Vibeke Henriette; Iversen, Eva Høgh; Donslund, Bjarke Skyum; Jørgensen, Karl Anker; Journal of the American Chemical Society 137 (2015) 1685–1691; doi:10.1021/ja512573q

data_4123357
_publ_section_title
;
 Organocatalytic enamine-activation of cyclopropanes for highly
 stereoselective formation of cyclobutanes.
;
_journal_issue                   4
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              1685
_journal_page_last               1691
_journal_paper_doi               10.1021/ja512573q
_journal_volume                  137
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C30 H30 Br N O10, 0.25(C3.72 H10.09 O)'
_chemical_formula_sum            'C30 H30 Br N O10'
_chemical_formula_weight         644.46
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-12-10
_audit_creation_method
;
Olex2 1.2
(compiled 2014.11.28 svn.r3106 for OlexSys, GUI svn.r4959)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.821(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.7370(16)
_cell_length_b                   27.527(3)
_cell_length_c                   15.2903(17)
_cell_measurement_reflns_used    2547
_cell_measurement_temperature    100
_cell_measurement_theta_max      16.23
_cell_measurement_theta_min      2.88
_cell_volume                     6170.8(12)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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      100
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           AgK\a
_diffrn_radiation_wavelength     0.56086
_diffrn_reflns_av_R_equivalents  0.0000
_diffrn_reflns_av_unetI/netI     0.1014
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            12675
_diffrn_reflns_point_group_measured_fraction_full 0.973
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        16.313
_diffrn_reflns_theta_max         16.313
_diffrn_reflns_theta_min         1.096
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.750
_exptl_absorpt_correction_T_max  0.8616
_exptl_absorpt_correction_T_min  0.6812
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1651 before and 0.0580 after correction.
The Ratio of minimum to maximum transmission is 0.7906.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_density_diffrn    1.387
_exptl_crystal_F_000             2656
_exptl_crystal_size_max          0.254
_exptl_crystal_size_mid          0.246
_exptl_crystal_size_min          0.089
_refine_diff_density_max         0.646
_refine_diff_density_min         -0.532
_refine_diff_density_rms         0.126
_refine_ls_abs_structure_details
;
 Flack x determined using 3741 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.004(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1311
_refine_ls_number_reflns         12662
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0862
_refine_ls_R_factor_gt           0.0629
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1160P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1664
_refine_ls_wR_factor_ref         0.1870
_reflns_Friedel_coverage         0.899
_reflns_Friedel_fraction_full    0.948
_reflns_Friedel_fraction_max     0.948
_reflns_number_gt                10201
_reflns_number_total             12662
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja512573q_si_002.cif
_cod_data_source_block           01_12_2014_kim
_cod_depositor_comments          'Adding full bibliography for 4123357.cif.'
_cod_original_cell_volume        6170.6(12)
_cod_database_code               4123357
_shelx_estimated_absorpt_t_max   0.936
_shelx_estimated_absorpt_t_min   0.832
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C14(H14), C25(H25), C28(H28), C33(H33), C42(H42), C59(H59), C66(H66),
 C86(H86), C87(H87), C90(H90), C99(H99), C102(H102), C114(H114), C122(H122),
 C130(H130), C131(H131)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C84(H84A,H84B), C92(H92A,H92B), C124(H12C,H12D), C134(H13D,
 H13E), C153(H15M,H15N)
2.c Aromatic/amide H refined with riding coordinates:
 C27(H27), C34(H34), C43(H43), C60(H60), C72(H72), C85(H85), C89(H89),
 C91(H91), C97(H97), C103(H103), C104(H104), C105(H105), C108(H108), C110(H110),
  C116(H116), C117(H117), C121(H121), C123(H123), C126(H126), C129(H129),
 C132(H132), C133(H133), C135(H135), C137(H137), C141(H141), C142(H142),
 C143(H143), C144(H144), C155(H155), C179(H179), C181(H181), C7AA(H7AA)
2.d Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C64(H64A,H64B,H64C), C71(H71A,H71B,H71C), C118(H11A,H11B,
 H11C), C119(H11D,H11E,H11F), C136(H13A,H13B,H13C), C149(H14A,H14B,H14C),
 C151(H15A,H15B,H15C), C156(H15J,H15K,H15L), C157(H15D,H15E,H15F), C158(H15G,
 H15H,H15I), C180(H18A,H18B,H18C), C161(H16A,H16B,H16C), C185(H18D,H18E,H18F),
 C2AA(H2AA,H2AB,H2AC), C5AA(H5AA,H5AB,H5AC), C6AA(H6AA,H6AB,H6AC), C4AA(H4AA,
 H4AB,H4AC), C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C8(H8A,H8B,H8C)
2.e Idealised tetrahedral OH refined as rotating group:
 O3AA(H3AA), O21(H21), O53(H53), O61(H61)
;
_shelx_res_checksum              7816
_shelx_hkl_checksum              43899
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'