A selective C-H insertion/olefination protocol for the synthesis of α-methylene-γ-butyrolactone natural products.
Lloyd, Matthew G.; D'Acunto, Mariantonietta; Taylor, Richard J. K.; Unsworth, William P.; Organic & biomolecular chemistry 14 (2016) 1641–1645; doi:10.1039/c5ob02579f

data_7154853
_publ_section_title
;
 A selective C-H insertion/olefination protocol for the synthesis of
 \a-methylene-\g-butyrolactone natural products.
;
_journal_issue                   5
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              1641
_journal_page_last               1645
_journal_paper_doi               10.1039/c5ob02579f
_journal_volume                  14
_journal_year                    2016
_chemical_formula_moiety         'C15 H20 O2'
_chemical_formula_sum            'C15 H20 O2'
_chemical_formula_weight         232.31
_chemical_melting_point          337.5(15)
_chemical_name_systematic
(3aRS,5aRS,9aSR,9bRS)-5a,9-dimethyl-3-methylene-3a,4,5,5a,6,7,9a,9b-octahydronaphtho[1,2-b]furan-2(3H)-one
_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     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-07-17
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-08-28 deposited with the CCDC.
2015-12-16 downloaded from the CCDC.
;
_cell_angle_alpha                89.047(4)
_cell_angle_beta                 89.710(4)
_cell_angle_gamma                89.044(4)
_cell_formula_units_Z            2
_cell_length_a                   7.4631(4)
_cell_length_b                   8.1068(4)
_cell_length_c                   10.7071(5)
_cell_measurement_reflns_used    2367
_cell_measurement_temperature    132(30)
_cell_measurement_theta_max      70.8450
_cell_measurement_theta_min      9.1030
_cell_volume                     647.61(6)
_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, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      132(30)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_details
;
  1 omega  -70.00   30.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -77.0000  120.0000 100

  2 omega   33.00  123.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   57.0000    0.0000 90

  3 omega   23.00  111.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000 -125.0000  -90.0000 88

  4 omega  -15.00   75.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -57.0000 -150.0000 90

  5 omega   33.00  123.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   57.0000   60.0000 90

  6 omega   35.00   94.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -25.0000    0.0000 59

  7 omega   36.00   92.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -37.0000    0.0000 56

  8 omega   35.00   94.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -25.0000  -90.0000 59

  9 omega   36.00   92.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -37.0000   60.0000 56

 10 omega   36.00  116.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000   60.0000 80

 11 omega   36.00  116.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  -60.0000 80

 12 omega   35.00   94.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -25.0000   90.0000 59

 13 omega   36.00  116.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000 -150.0000 80

 14 omega   86.00  178.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   50.0000  120.0000 92

 15 omega   38.00  138.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000 -180.0000 100

 16 omega  -30.00   70.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   77.0000  -90.0000 100

 17 omega   24.00   55.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   77.0000  -90.0000 31

 18 omega   33.00  123.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   57.0000 -150.0000 90

 19 omega    1.00   47.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       55.4856  -37.0000   90.0000 46

 20 omega   34.00   60.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       55.4856   19.0000  -60.0000 26

 21 omega   79.00  123.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       55.4856   19.0000  -60.0000 44

 22 omega   31.00   76.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       55.4856 -125.0000  120.0000 45

 23 omega   35.00   84.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -25.0000  150.0000 49

 24 omega   40.00   67.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -91.0000    0.0000 27

 25 omega   60.00   89.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -50.0000 -120.0000 29

 26 omega   52.00  107.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000   60.0000 55

 27 omega  120.00  152.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000 -180.0000 32

 28 omega   80.00  126.00   1.0000   32.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   25.0000  -60.0000 46
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.2021971000
_diffrn_orient_matrix_UB_12      0.0240265000
_diffrn_orient_matrix_UB_13      -0.0216011000
_diffrn_orient_matrix_UB_21      0.0286164000
_diffrn_orient_matrix_UB_22      0.0073133000
_diffrn_orient_matrix_UB_23      0.1421801000
_diffrn_orient_matrix_UB_31      0.0303529000
_diffrn_orient_matrix_UB_32      -0.1884193000
_diffrn_orient_matrix_UB_33      0.0051672000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54181
_diffrn_reflns_av_R_equivalents  0.0157
_diffrn_reflns_av_unetI/netI     0.0212
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            4954
_diffrn_reflns_theta_full        71.01
_diffrn_reflns_theta_max         71.01
_diffrn_reflns_theta_min         4.13
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.608
_exptl_absorpt_correction_T_max  0.983
_exptl_absorpt_correction_T_min  0.909
_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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.191
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             252
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Chloroform/diethyl ether'
_exptl_crystal_size_max          0.2239
_exptl_crystal_size_mid          0.1846
_exptl_crystal_size_min          0.0284
_refine_diff_density_max         0.273
_refine_diff_density_min         -0.188
_refine_diff_density_rms         0.036
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     176
_refine_ls_number_reflns         2399
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0439
_refine_ls_R_factor_gt           0.0395
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0623P)^2^+0.1306P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1080
_refine_ls_wR_factor_ref         0.1119
_reflns_number_gt                2129
_reflns_number_total             2399
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c5ob02579f2.cif
_cod_data_source_block           rjkt1516
_cod_depositor_comments
;
The following automatic conversions were performed:

'_chemical_melting_point' value '336-339' was changed to '337.5(15)'
- the average value was taken and precision was estimated.

Automatic conversion script
Id: cif_fix_values 4268 2015-11-12 08:31:59Z antanas 

 Adding full bibliography for 7154852--7154854.cif.
;
_cod_database_code               7154853
_chemical_oxdiff_formula         'C15 H20 O2'
_chemical_oxdiff_usercomment     'Matthew MGL/07/43-P'
_reflns_odcompleteness_completeness 98.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Restrained distances
 C9-C10 \\sim C9A-C10
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(C6) = Uanis(C6A)
Uanis(C7) = Uanis(C7A)
Uanis(C9) = Uanis(C9A)
Uanis(C8A) = Uanis(C8)
Uanis(C14A) = Uanis(C14)
Uanis(C5A) = Uanis(C5)
4. Others
 Sof(H4BC)=Sof(H4BD)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C6)=Sof(C7)=Sof(H7A)=
 Sof(H7B)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(C9)=Sof(H9)=Sof(H11A)=Sof(C14)=
 Sof(H14A)=Sof(H14B)=Sof(H14C)=1-FVAR(1)
 Sof(H4AA)=Sof(H4AB)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(C6A)=Sof(C7A)=Sof(H7AA)=
 Sof(H7AB)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(C9A)=Sof(H9A)=Sof(H11)=Sof(C14A)=
 Sof(H14D)=Sof(H14E)=Sof(H14F)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C3(H3), C11(H11A), C11(H11), C12(H12)
5.b Secondary CH2 refined with riding coordinates:
 C4(H4BC,H4BD), C4(H4AA,H4AB), C5(H5A,H5B), C5A(H5AA,H5AB), C7(H7A,H7B),
 C7A(H7AA,H7AB), C8(H8A,H8B), C8A(H8AA,H8AB)
5.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C9A(H9A)
5.d X=CH2 refined with riding coordinates:
 C13(H13A,H13B)
5.e Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C14A(H14D,H14E,H14F), C15(H15A,H15B,H15C)
;
_olex2_date_sample_data_collection 2015-07-08
_olex2_exptl_crystal_mounting_method 'oil on micromount'
_olex2_submission_special_instructions 'No special instructions were received'