SmCp<sup>R</sup><sub>2</sub>-mediated cross-coupling of allyl and propargyl ethers with ketoesters and a telescoped approach to complex cycloheptanols.
Plesniak, Mateusz P.; Just-Baringo, Xavier; Ortu, Fabrizio; Mills, David P.; Procter, David J.; Chemical communications (Cambridge, England) 52 (2016) 13503–13506; doi:10.1039/c6cc07318b

data_7125177
_publ_section_title
;
 SmCp<sup>R</sup><sub>2</sub>-mediated cross-coupling of allyl and
 propargyl ethers with ketoesters and a telescoped approach to complex
 cycloheptanols.
;
_journal_issue                   92
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              13503
_journal_page_last               13506
_journal_paper_doi               10.1039/c6cc07318b
_journal_volume                  52
_journal_year                    2016
_chemical_formula_moiety         'C27 H51 O Si4 Sm'
_chemical_formula_sum            'C27 H51 O Si4 Sm'
_chemical_formula_weight         654.39
_chemical_properties_physical    ', Air-sensitive,Moisture-sensitive'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           36
_space_group_name_Hall           'C 2c -2'
_space_group_name_H-M_alt        'C m c 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-07-15
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2016-08-29 deposited with the CCDC.
2016-10-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.6326(6)
_cell_length_b                   13.7770(7)
_cell_length_c                   21.1559(14)
_cell_measurement_reflns_used    2085
_cell_measurement_temperature    150.02(10)
_cell_measurement_theta_max      24.5770
_cell_measurement_theta_min      3.9020
_cell_volume                     3390.5(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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_environment      N~2~
_diffrn_ambient_temperature      150.02(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0714
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_details
;
  1 omega  -32.00   69.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       19.4509    0.0000  -30.0000 101

  2 omega  -11.00   90.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       19.4509   77.0000  -60.0000 101
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0254661000
_diffrn_orient_matrix_UB_12      0.0179139000
_diffrn_orient_matrix_UB_13      -0.0299488000
_diffrn_orient_matrix_UB_21      0.0218024000
_diffrn_orient_matrix_UB_22      0.0189516000
_diffrn_orient_matrix_UB_23      -0.0356533000
_diffrn_orient_matrix_UB_31      -0.0007382000
_diffrn_orient_matrix_UB_32      -0.0551118000
_diffrn_orient_matrix_UB_33      -0.0219587000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0577
_diffrn_reflns_av_unetI/netI     0.0913
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            6444
_diffrn_reflns_point_group_measured_fraction_full 0.790
_diffrn_reflns_point_group_measured_fraction_max 0.788
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.364
_diffrn_reflns_theta_min         3.503
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.889
_exptl_absorpt_correction_T_max  0.981
_exptl_absorpt_correction_T_min  0.908
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.282
_exptl_crystal_description       block
_exptl_crystal_F_000             1356
_exptl_crystal_size_max          0.3658
_exptl_crystal_size_mid          0.2016
_exptl_crystal_size_min          0.0521
_refine_diff_density_max         1.399
_refine_diff_density_min         -0.673
_refine_diff_density_rms         0.118
_refine_ls_abs_structure_details
;
 Flack x determined using 666 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.48(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     276
_refine_ls_number_reflns         2876
_refine_ls_number_restraints     470
_refine_ls_restrained_S_all      1.001
_refine_ls_R_factor_all          0.0673
_refine_ls_R_factor_gt           0.0530
_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^)+(0.0401P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0976
_refine_ls_wR_factor_ref         0.1050
_reflns_Friedel_coverage         0.540
_reflns_Friedel_fraction_full    0.574
_reflns_Friedel_fraction_max     0.570
_reflns_number_gt                2449
_reflns_number_total             2876
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6cc07318b2.cif
_cod_data_source_block           5b
_cod_database_code               7125177
_manchester_internal_coll_name   adpm104
_manchester_internal_coll_client MP/DP/DPM
_manchester_internal_coll_type   custom
_manchester_internal_coll_frame_time 6s
_manchester_internal_coll_frame_width 1
_manchester_internal_coll_frame_method '\w scans'
_manchester_internal_coll_user   MP
_manchester_internal_coll_date   25/11/2014
_manchester_internal_process_user MP
_manchester_internal_process_date 25/11/2014
_manchester_internal_solution_user FO
_manchester_internal_solution_date 15/07/2015
_manchester_internal_refinement_user FO
_manchester_internal_refinement_date 21/07/2015
_manchester_internal_validation_user FO
_manchester_internal_validation_date 21/07/2015
_manchester_internal_archive_date 21/07/2015
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'Sm1 C26 Si4 O1'
_reflns_odcompleteness_completeness 99.07
_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. Restrained distances
 O1-C12 = O1-C16
 1.47 with sigma of 0.02
 C13-C12 = C16-C14
 1.52 with sigma of 0.02
 C13-C14
 1.52 with sigma of 0.02
 C3A-C2 = C3A-C5 = C1A-C5 = C1A-C2A = C2A-C2
 1.4 with sigma of 0.02
 C1A-C5 \\sim C1A-C2A \\sim C2A-C2 \\sim C3A-C2 \\sim C3A-C5
 with sigma of 0.02
 C1A-C2A \\sim C1-C5 \\sim C1-C2 \\sim C2A-C2 \\sim C3-C2 \\sim C3A-C2 \\sim
C3-C4 \\sim C3A-C5 \\sim C5-C4 ~
 C1A-C5
 with sigma of 0.002
3. Restrained planarity
 C5, C1, C2, C3, C4
 with sigma of 0.1
 C2, C3A, C5, C1A, C2A
 with sigma of 0.1
4. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: Si1A(0.5) Si2(0.5) Si1(0.5) C1(0.5) C3(0.5) C6(0.5) H6A(0.5)
 H6B(0.5) H6C(0.5) C8(0.5) H8A(0.5) H8B(0.5) H8C(0.5) C9(0.5) H9A(0.5) H9B(0.5)
 H9C(0.5) C12(0.5) H12A(0.5) H12B(0.5) C7A(0.5) H7AA(0.5) H7AB(0.5) H7AC(0.5)
 C11(0.5) H11A(0.5) H11B(0.5) H11C(0.5) C7(0.5) H7A(0.5) H7B(0.5) H7C(0.5)
 C6A(0.5) H6AA(0.5) H6AB(0.5) H6AC(0.5) C10(0.5) H10A(0.5) H10B(0.5) H10C(0.5)
 C8A(0.5) H8AA(0.5) H8AB(0.5) H8AC(0.5) Si2A(0.5) C10A(0.5) H10D(0.5) H10E(0.5)
 H10F(0.5) C11A(0.5) H11D(0.5) H11E(0.5) H11F(0.5) C2A(0.5) H2A(0.5) C1A(0.5)
 H5B(0.5) H5A(0.5) C3A(0.5) H3A(0.5) H2(0.5) C9A(0.5) H9AA(0.5) H9AB(0.5)
 H9AC(0.5) C14(0.5) H14A(0.5) H14B(0.5) C13(0.5) H13A(0.5) H13B(0.5) C16(0.5)
 H16A(0.5) H16B(0.5)
7.a Ternary CH refined with riding coordinates:
 C5(H5B), C5(H5A), C3A(H3A), C2(H2)
7.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C14(H14A,H14B), C13(H13A,H13B), C16(H16A,H16B)
7.c Me refined with riding coordinates:
 C11A(H11D,H11E,H11F)
7.d Aromatic/amide H refined with riding coordinates:
 C4(H4), C2A(H2A)
7.e Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C7A(H7AA,H7AB,H7AC),
 C11(H11A,H11B,H11C), C7(H7A,H7B,H7C), C6A(H6AA,H6AB,H6AC), C10(H10A,H10B,H10C),
  C8A(H8AA,H8AB,H8AC), C10A(H10D,H10E,H10F), C9A(H9AA,H9AB,H9AC)
;
_shelx_res_checksum              50558
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'