Synthesis and transformations of metallacycles 41.* Cyclomagnesiation of O-containing 1,2-dienes with Grignard reagents in the presence of Cp 2TiCl2

Article abstract of DOI:10.1007/s11172-012-0269-1

A Cp₂TiCl₂-catalyzed intermolecular homocyclomagnesiation of O-containing 1,2-dienes and cross-cyclomagnesiation of O-containing 1,2-dienes with aliphatic 1,2-dienes of cyclic and acyclic structure have been accomplished using Grignard reagents, which led to mono- and bicyclic organomagnesium compounds in 61-94% yields.

Full text of DOI:10.1007/s11172-012-0269-1

Russian Chemical Bulletin, International Edition, Vol. 61, No. 10, pp. 1943—1949, October, 2012
1943
Synthesis and transformations of metallacycles
41.* Cyclomagnesiation of Oꢀcontaining 1,2ꢀdienes with Grignard reagents
in the presence of Cp2TiCl2
V. A. D´yakonov, A. A. Makarov, E. Kh. Makarova, L. M. Khalilov, and U. M. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences,
141 prosp. Oktyabrya, 450075 Ufa, Russian Federation.
Fax: +7 (347) 284 2750. Eꢀmail: DyakonovVA@rambler.ru
A Cp2TiCl2ꢀcatalyzed intermolecular homocyclomagnesiation of Oꢀcontaining 1,2ꢀdienes
and crossꢀcyclomagnesiation of Oꢀcontaining 1,2ꢀdienes with aliphatic 1,2ꢀdienes of cyclic
and acyclic structure have been accomplished using Grignard reagents, which led to monoꢀ and
bicyclic organomagnesium compounds in 61—94% yields.
Key words: organomagnesium compounds, metal complex catalysis, magnesacyclopentane,
1,2ꢀdienes, 1Z,5Zꢀdienes, cyclomagnesiation.
Earlier,2—4 we have shown that aliphatic 1,2ꢀdienes
Scheme 1
react with EtMgBr in the presence of Mg and Cp2TiCl2
with the formation of 2,5ꢀdialkylidenemagnesacycloꢀ
pentanes, which after acid hydrolysis were converted to
symmetric 1Z,5Zꢀdienes in ~90% yields. The reaction inꢀ
dicated is used in the development of efficient methods for
the synthesis of substituted symmetric 1Z,5Zꢀdienes5 and
gigantic hydrocarbon macrocycles.6
In continuation of these studies, as well as in order to
develop efficient methods for the preparation of functionꢀ
ally substituted 1Z,5Zꢀdiene compounds, which are of exꢀ
clusive interest as key synthons in the synthesis of practiꢀ
cally important insect pheromones,7 fragrant substances,8
and biologically active compounds of natural origin,9,10
we have studied cyclomagnesiation of oxygenꢀcontaining
1,2ꢀdienes using Grignard reagents in the presence of
Cp2TiCl2.
We found that allenic and homoallenic alcohols with
unprotected hydroxyl group, as well as their trimethylsilyl
ethers, cannot be involved in the cyclomagnesiation reacꢀ
[Ti] = Cp2TiCl
X = H (3), D (4)
2
tion.3 At the same time, allenic alcohols 1a—d with the
pyranyl or benzyl protection, in which the 1,2ꢀdiene group
is separated from the oxygen atom by two or more methꢀ
yl groups, react with excess EtMgBr in the presence
of Cp2TiCl2 (5 mol.%), giving 2,5ꢀdialkylidenemagnesaꢀ
cyclopentanes 2 in 68—84% yields. The latter after acid
hydrolysis or deuterolysis give the corresponding symꢀ
metric Oꢀcontaining 1Z,5Zꢀdiene compounds 3 and 4
(Scheme 1).
1—4
a
b
n
2
2
R
THP
Bn
1—4
c
d
n
4
6
R
THP
THP
(1D and 2D NMR spectroscopy, IR spectroscopy, mass
spectrometry).
The formation of substituted 3,6ꢀdideuteroꢀ2Z,6Zꢀ
dienes 4 as a result of deuterolysis of the reaction mixtures
unambiguously indicates the presence in the starting orgaꢀ
nomagnesium compound (OMC) 2 of two Mg—C bonds.
The cisꢀconfiguration of substituents at the double bonds
in the 1,5ꢀdienes obtained can be suggested from the preꢀ
sence of the upfield signals for the internal allylic carbon
The structures of compounds 3 and 4 were reliably
confirmed by modern methods of spectroscopic analysis
* For Part 40, see Ref. 1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1928—1934, October, 2012.
1066ꢀ5285/12/6110ꢀ1943 © 2012 Springer Science+Business Media, Inc.

1944
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 10, October, 2012
D´yakonov et al.
atoms (C(4)) = (C(5))  27 in the 13C NMR spectrum,
indicating the presence of the cisꢀinteractions with atoms
C(1) and C(8).11
The vicinal spinꢀspin coupling constants of the proꢀ
tons at C(3) and C(6) (d, 3J = 11 Hz; t, 3J = 7 Hz) for the
hydrolysis products 3 confirm the cisꢀarrangement of the
hydrogen atoms at the double bonds.12
The use of other Grignard reagents instead of EtMgBr,
for example, EtMgCl, PriMgBr, BuMgBr obtained in diꢀ
ethyl ether, did not influence the yields and selectivity of
the formation of the target OMC 2.
These facts allowed us to suggest a possibility to synꢀ
thesize unsymmetric functionally substituted magnesacyꢀ
clopentanes by the crossꢀcyclomagnesiation of structuralꢀ
ly different 1,2ꢀdienes. It is necessary to note that such an
approach have been earlier successfully used in the coꢀ
reaction of cyclononaꢀ1,2ꢀdiene and terminal 1,2ꢀdienes
with the formation of bicyclic OMC in up to 85% yields.3
In fact, the reaction of an equimolar mixture of cycloꢀ
nonaꢀ1,2ꢀdiene (5) and 2ꢀ(pentaꢀ3,4ꢀdienꢀ1ꢀyloxy)tetraꢀ
hydropyran (1a) with EtMgBr in the presence of Mg and
Cp2TiCl2 predominantly led to the formation of bicyclic
OMC 6a, which after hydrolysis and deuterolysis was conꢀ
verted to the corresponding cyclononene derivatives 7a,
8a in 54% yield (Scheme 2).
The optimization of conditions for the synthesis of
the target OMC 6a by the change in the ratio of the reacꢀ
tion components allowed us to select such conditions
(1 : 5 : EtMgBr : Mg : [Ti] = 10 : 15 : 30 : 32 : 1; Et2O, 6 h,
20—22 C), in which OMC 6a and 6b were formed
in 80 and 87% yields, respectively, with the yields of
homocyclomagnesiation products totaling lower than
5—10%.
Similar investigations directed on the optimization of
conditions for the crossꢀcyclomagnesiation of Oꢀcontainꢀ
ing 1,2ꢀdienes with terminal alkylꢀ and arylꢀsubstitutꢀ
ed allenes 9 in the presence of EtMgBr and Cp2TiCl2
(1 : 9 : EtMgBr : Mg : [Ti] = 10 : 12 : 40 : 32 : 0.5; Et2O,
6 h, 20—22 C) led to the exclusive preparation of unsymꢀ
metric OMC 10 in >80% yields (Scheme 3).
Scheme 3
Scheme 2
[Ti] = Cp2TiCl
2
X = H (11), D (12)
n
2
2
2
3
R
R´
n
4
4
6
R
THP
THP C6H13
THP Bu
R´
Bu
a
b
c
d
THP C6H13
Bn
THP
THP C12H25
e
f
g
C6H13
Bn
In this case, the absence of side products of homoꢀ
cyclomagnesiation of aliphatic 1,2ꢀdienes 9 was explained
by the running the reaction in diethyl ether, in which, as it
has been shown earlier,2,13 no formation of 2,5ꢀdialkyꢀ
lidenemagnesacyclopentanes took place.
A small excess of aliphatic 1,2ꢀdiene 9 virtually comꢀ
pletely blocked the formation of OMC 2, whose yields
under the reaction conditions were ~2—5%.
[Ti] = Cp2TiCl
2
The same pattern was observed for the cases when both
the length of the alkyl substituent in the aliphatic allenes 9
and the number of the methylene units between the 1,2ꢀdiꢀ
ene system and the oxygen atom in the Oꢀcontaining
1,2ꢀdiene 1, were increased.
n = 2: R = THP (a), Bn (b)
These conditions, besides the target OMC 6a, also gave
the product of homocyclomagnesiation of cyclononadiene3
and Oꢀcontaining allene 1a in ~20—25% yield.

TiꢀCatalyzed cyclomagnesiation of allenes
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 10, October, 2012
1945
(50 mmol), dicyclohexylamine (38 mmol) were placed in a 250ꢀmL
glass reactor equipped with a reflux condenser with stirring unꢀ
der dry argon at ~20 C, followed by the addition of CuI
(10 mmol). The reaction mixture was refluxed with stirring for
8 h, then cooled to 20—22 C and filtered. The filtrate was conꢀ
centrated in vacuo, the residue was washed with 5% solution of
HCl in H2O. The reaction products were extracted with diethyl
ether, the extract was dried with MgSO4, the solvent was evapoꢀ
rated, the residue was subjected to chromatography on a column
(SiO2, eluent light petroleum—EtOAc (10 : 1)). The yields of
Oꢀcontaining allenes 1 were 70—75%.
Homocyclomagnesiation of Oꢀcontaining 1,2ꢀdienes (1a—d)
using RMgX (R = Et, Pri, Bu; X = Cl, Br) in the presence of
metallic Mg and a Cp2TiCl2 catalyst. Diethyl ether (10 mL),
1,2ꢀdiene (10 mmol), RMgX (20 mmol, 1.5 M solution in Et2O),
Mg powder (24 mmol), and Cp2TiCl2 (0.5 mmol) were placed in
a glass reactor with stirring under dry argon (~0 C). The temꢀ
perature of the reaction mixture was increased to 20—22 C and
stirring was continued for 6—8 h. To identify the substituted
magnesacyclopentanes by their hydrolysis or deuterolysis prodꢀ
ucts, the reaction mixture were treated with 5% solution of HCl
(DCl) in H2O (D2O). The reaction products were extracted with
diethyl ether, the extracts were dried with MgSO4, the solvent
was evaporated, the residue was subjected to chromatography on
a column (SiO2, eluent light petroleum—EtOAc (50 : 1)).
2,2´ꢀ[Decaꢀ3Z,7Zꢀdienꢀ1,10ꢀdiylbis(oxy)]bistetrahydroꢀ2Hꢀ
pyran (3a). The yield was 69%, nD20 1.4969, Rf = 0.61. Found (%):
C, 70.05; H, 9.96. Calculated (%): C, 70.97; H, 10.12. MS MALDI
TOF: found m/z 338.5. C20H34O4. Calculated: M = 338.5. IR,
/cm–1: 648, 733, 909, 981, 1030, 1076, 1136, 1323, 1440, 2247,
2871, 2945. 1H NMR, : 1.48—1.84 (m, 12 H, 6 CH2); 2.10—2.11
(m, 4 H, 2 CH2CH=C); 2.30—2.40 (m, 4 H, 2 CH2CH=C);
3.38—3.87 (m, 8 H, 2 CH2—O); 4.58 (t, 2 H, 2 O—CH—O,
J = 3.6 Hz); 5.36—5.55 (m, 4 H, 4 HC=). 13C NMR, : 19.54
(C(13), C(18)); 25.46 (C(14), C(19)); 27.32 (C(5), C(6));
27.97 (C(2), C(9)); 30.68 (C(12), C(17)); 62.20 (C(15), C(20));
67.00 (C(1), C(10)); 98.66 (C(11), C(16)); 126.08 (C(3), C(8));
131.05 (C(4), C(7)).
The studies performed resulted in obtaining a large
series of OMC 10, which were of interest as the starting
reagents for the poorly available unsymmetric functionalꢀ
ly substituted 1Z,5Zꢀdienes of a required structure.
For example, 1Z,5Zꢀdiene 11g, formed in 94% yield
after hydrolysis of OMC 10, is an intermediate product in
the synthesis of practically important pheromone of cotꢀ
ton pink boll worm Pectinophora gossypiella, which has
been obtained earlier14 in seven steps in ~5% yield.
In conclusion, an intermolecular homocyclomagnesiꢀ
ation of Oꢀcontaining 1,2ꢀdienes and crossꢀcyclomagneꢀ
siation of Oꢀcontaining allenes with aliphatic 1,2ꢀdienes
of cyclic and acyclic structure were accomplished for the
first time using Grignard reagents upon the action of
Cp2TiCl2 to furnish functionally substituted monoꢀ and
bicyclic organomagnesium compounds, possessing wide
synthetic potential in the synthesis of practically imporꢀ
tant functionally substituted 1Z,5Zꢀdienes of a desired
structure.
Experimental
Chromatographic analysis was performed on a Shimadzu
GCꢀ9A instrument, using a 2000×2ꢀmm column with Silicon
SEꢀ30 (5%) on Chromaton NꢀAWꢀHMDS (0.125—0.160 mm)
as a stationary phase, carrier gas helium (30 mL min–1), the
temperature was programmed from 50 to 300 C at the speed of
8 C min–1. 1H and 13C NMR spectra were recorded on a Bruker
Avanceꢀ400 spectrometer (13C, 100 MHz; 1H, 400 MHz) in
CDCl3, chemical shifts were measured relative to Me4Si. Chroꢀ
matoꢀmass spectrometric analysis of compounds was performed
on a Shimadzu GCMSꢀQP2010 Plus instrument (SLBꢀ5ms
60000×0.25 mm×0.25 m glass capillary column (Supelco, USA),
carrier gas helium, the temperature was programmed from 40 to
280 C at the speed of 5 C min–1, the temperature of injector
280 C, the temperature of the source of ions 200 C, 70 eV).
Mass spectra were recorded on a MALDI TOF/TOF Autoꢀ
flexꢀIII Bruker instrument with the matrix of 2,5ꢀdihydroxyꢀ
benzoic acids (2,5ꢀDHB) and ꢀcyanoꢀ4ꢀhydroxycinnamic
acids (HCCA) in the reflective mode with recording positive ions.
Elemental analysis was performed on Karlo Erba 1106 elemenꢀ
tal analyzer. The product yields were determined using GLC
analysis. Purity of the reaction products was monitored on Siluꢀ
fol UVꢀ254 plates, visualizing in the iodine vapors. Reactions
with organometallic compounds were performed under dry arꢀ
gon. Solvents were dried and distilled before use. The compound
Cp2TiCl2 was commercially available from Aldrich. Ether solꢀ
vents were distilled over LiAlH4 directly before use. Solutions of
RMgX in Et2O were obtained as described earlier.15 Pentaꢀ3,4ꢀ
dienꢀ1ꢀol was synthesized according to the known procedure.16
Hexaꢀ4,5ꢀdienꢀ1ꢀol, heptaꢀ5,6ꢀdienꢀ1ꢀol, and nonaꢀ7,8ꢀdienꢀ
1ꢀol were obtained according to a modified procedure17 and
identified by comparison with the known literature data.18,19
Allene alcohols were protected by transformation to the correꢀ
sponding ethers as described earlier.20
2,2´ꢀ[4,7ꢀDideuterodecaꢀ3Z,7Zꢀdienꢀ1,10ꢀdiylbis(oxy)]ꢀ
bistetrahydroꢀ2Hꢀpyran (4a). The yield was 68%, Rf = 0.61.
Found (%): C, 70.01; H + D, 10.49. C20H32D2O4. Calculatꢀ
ed (%): C, 70.55; H, 9.47; D, 1.18. MS (EI), m/z: 340 [M]+. IR,
/cm–1: 649, 733, 908, 981, 1030, 1075, 1136, 1323, 1441, 2175
1
(C—D), 2247, 2870, 2945. H NMR, : 1.50—1.88 (m, 12 H,
6 CH2); 2.03—2.19 (m, 4 H, 2 CH2CH=C); 2.25—2.36 (m, 4 H,
2 CH2CH=C); 3.36—3.88 (m, 8 H, 4 CH2—O); 4.58 (t, 2 H,
2 O—CH—O, J = 3.6 Hz); 5.40 (t, 2 H, 2 HC=CD, J = 6.8 Hz).
13C NMR, : 19.56 (C(13), C(18)); 25.47 (C(14), C(19)); 27.21
(C(5), C(6)); 27.95 (C(2), C(9)), 30.69 (C(12), C(17)), 62.21
(C(15), C(20)), 67.01 (C(1), C(10)), 98.68 (C(11), C(16)), 125.95
(C(3), C(8)), 130.71 (t, C(4), C(7), JC,D = 24 Hz).
1,1´ꢀ[Decaꢀ3Z,7Zꢀdienꢀ1,10ꢀdiylbis(oxymethylene)]dibenzꢀ
ene (3b). The yield was 71%, nD20 1.5458, Rf = 0.59. Found (%):
C, 81.95; H, 8.34. Calculated (%): C, 82.24; H, 8.63. MS MALDI
TOF: found m/z 350.5. C24H30O2. Calculated: M = 350.5. IR,
/cm–1: 697, 735, 1028, 1101, 1204, 1361, 1453, 1495, 2854,
1
2929, 3028. H NMR, : 2.21—2.29 (m, 4 H, 2 CH2CH=C);
2.42—2.49 (m, 4 H, 2 CH2CH=C); 3.56 (t, 4 H, 2 CH2—O,
J = 6.8 Hz); 4.60 (s, 4 H, 2 CH2Ph); 5.51—5.60 (m, 4 H, 4 HC=);
7.36—7.43 (m, 10 H, 2 Ph). 13C NMR, : 27.46 (C(5), C(6));
28.13 (C(2), C(9); 70.06 (C(1),C(10)); 72.94 (C(11), C(18));
Oxygenꢀcontaining allenes (general procedure). Alkynol
(2ꢀpropynꢀ1ꢀol, 3ꢀbutynꢀ1ꢀol, 4ꢀpentynꢀ1ꢀol, 5ꢀhexynꢀ1ꢀol,
7ꢀoctynꢀ1ꢀol) (20 mmol), dioxane (100 mL), paraformaldehyde

1946
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 10, October, 2012
D´yakonov et al.
126.19 (C(15), C(22)); 127.43 (C(14), C(16), C(21), C(23));
127.58 (C(3), C(8)); 128.43 (C(13), C(17), C(20), C(24)); 131.19
(C(4), C(7)); 138.64 (C(19)).
IR, /cm–1: 815, 844, 869, 905, 969, 1034, 1077, 1122, 1136,
1182, 1200, 1259, 1275, 1283, 1322, 1352, 1384, 1440, 1464,
2175 (C—D), 2855, 2936, 3005. 1H NMR, : 1.24—1.32 (m, 4 H,
2 CH2); 1.48—1.56 (m, 12 H, 6 CH2); 1.62—1.84 (m, 12 H,
6 CH2); 1.98—2.02 (m, 8 H, 4 CH2CH=C); 3.30—3.78 (m, 8 H,
4 CH2—O); 4.57 (t, 2 H, 2 O—CH—O, J = 4 Hz); 5.35 (t, 2 H,
2 HC=CD, J = 7 Hz). 13C NMR, : 19.60 (C(21), C(26));
25.54 (C(22), C(27)); 26.18 (C(3), C(16)); 27.15 (C(6), C(13));
27.35 (C(9), C(10)); 29.18 (C(4), C(15)); 29.72 (C(2), C(17));
30.62 (C(20), C(25)); 30.71 (C(5), C(14)); 62.18 (C(23), C(28));
67.57 (C(1), C(18)); 98.75 (C(19), C(24)); 128.87 (t, C(8), C(11),
JC,D = 23.5 Hz); 130.14 (C(7), C(12)).
Crossꢀcyclomagnesiation of Oꢀcontaining 1,2ꢀdienes with
cyclononaꢀ1,2ꢀdiene using EtMgBr in the presence of metallic
Mg and a Cp2TiCl2 catalyst (general procedure). Diethyl ether
(10 mL), Oꢀcontaining 1,2ꢀdiene (10 mmol), cyclononaꢀ1,2ꢀ
diene (15 mmol), EtMgBr (30 mmol, 1.5 M solution in Et2O),
Mg powder (32 mmol), and Cp2TiCl2 (1 mmol) were placed in
a glass reactor with stirring under dry argon (~0 C). The temꢀ
perature of the reaction mixture was increased to 20—22 C and
stirring was continued for 6—8 h. To identify the substituted
unsymmetric magnesacyclopentanes by their hydrolysis or
deuterolysis products, the reaction mixtures were treated with
5% solution of HCl (DCl) in H2O (D2O). The reaction products
were extracted with diethyl ether, the extracts were dried with
MgSO4, the solvent was evaporated, the residue was subjected
to chromatography on a column (SiO2, eluent light petroꢀ
leum—EtOAc (50 : 1)).
Crossꢀcyclomagnesiation of Oꢀcontaining 1,2ꢀdienes with terꢀ
minal 1,2ꢀdienes using EtMgBr in the presence of metallic Mg and
a Cp2TiCl2 catalyst (general procedure). Diethyl ether (10 mL),
Oꢀcontaining 1,2ꢀdiene (10 mmol), cyclononaꢀ1,2ꢀdiene or the
corresponding aliphatic 1,2ꢀdiene (12 mmol), EtMgBr (40 mmol,
1.5 M solution in Et2O), Mg powder (32 mmol), and Cp2TiCl2
(0.5 mmol) were placed in a glass reactor with stirring under dry
argon (~0 C). The temperature of the reaction mixture was
increased to 20—22 C and stirring was continued for 6—8 h. To
identify the substituted unsymmetric magnesacyclopentanes by
their hydrolysis or deuterolysis products, the reaction mixture
were treated with 5% solution of HCl (DCl) in H2O (D2O). The
reaction products were extracted with diethyl ether, the extracts
were dried with MgSO4, the solvent was evaporated, the residue
was subjected to chromatography on a column (SiO2, eluent
light petroleum—EtOAc (50 : 1)).
1,1´ꢀ[4,7ꢀDideuterodecaꢀ3Z,7Zꢀdienꢀ1,10ꢀdiylbis(oxymethꢀ
ylene)]dibenzene (4b). The yield was 73%, Rf = 0.59. Found (%):
C, 81.58; H + D, 9.02. C24H28D2O2. Calculated (%): C, 81.77;
H, 8.01; D, 1.14. MS (EI), m/z: 352 [M]+. IR, /cm–1: 697, 735,
1028, 1101, 1205, 1361, 1453, 1495, 2180 (C—D), 2856, 2929,
3027. 1H NMR, : 2.21—2.31 (m, 4 H, 2 CH2CH=C); 2.42—2.47
(m, 4 H, 2 CH2CH=C); 3.58 (t, 4 H, 2 CH2—O, J = 6.8 Hz);
4.61 (s, 4 H, 2 CH2Ph); 5.45 (t, 2 H, 2 HC=CD, J = 6.8 Hz);
7.34—7.45 (m, 10 H, 2 Ph). 13C NMR, : 27.48 (C(5), C(6));
28.15 (C(2), C(9)); 70.04 (C(1), C(10)); 72.96 (C(11), C(18));
126.20 (C(15), C(22)); 127.45 (C(14), C(16), C(21), C(23));
127.59 (C(3), C(8)); 128.42 (C(13), C(17), C(20), C(24)); 130.91
(t, C(4), C(7), JC,D = 22.5 Hz); 138.62 (C(19)).
2,2´ꢀ[Tetradecaꢀ5Z,9Zꢀdienꢀ1,14ꢀdiylbis(oxy)]bistetrahydroꢀ
20
2Hꢀpyran (3c). The yield was 78%, nD 1.4969, Rf = 0.56.
Found (%): C, 72.91; H, 10.15. Calculated (%): C, 73.05;
H, 10.73. MS MALDI TOF: found m/z 394.6. C24H42O4. Calꢀ
culated: M = 394.6. IR, /cm–1: 647, 733, 908, 981, 1030, 1078,
1136, 1323, 1440, 2245, 2871, 2948. 1H NMR, : 1.34—1.81
(m, 20 H, 10 CH2); 1.99—2.11 (m, 8 H, 4 CH2CH=C); 3.30—3.84
(m, 8 H, 4 CH2—O); 4.52 (t, 2 H, 2 O—CH—O, J = 3.6 Hz);
5.29—5.36 (m, 4 H, 4 HC=). 13C NMR, : 19.56 (C(17), C(22));
25.47 (C(18), C(23)); 26.33 (C(3), C(12)); 26.99 (C(7), C(8));
27.32 (C(4), C(11)); 29.31 (C(2), C(13)); 30.70 (C(16), C(21));
62.09 (C(19), C(24)); 67.34 (C(1), C(14)); 98.66 (C(15), C(20));
129.34 (C(6), C(9)); 129.90 (C(5), C(10)).
2,2´ꢀ[4,7ꢀDideuterotetradecaꢀ5Z,9Zꢀdienꢀ1,14ꢀdiylbis(oxy)]ꢀ
bistetrahydroꢀ2Hꢀpyran (4c). The yield was 77%, Rf = 0.56.
Found (%): C, 72.25; H + D, 11.04. C24H40D2O4. Calculatꢀ
ed (%): C, 72. 68; H, 10.17; D, 1.02. MS (EI), m/z: 396 [M]+.
IR, /cm–1: 647, 734, 908, 980, 1030, 1078, 1136, 1323, 1441,
2170 (C—D), 2245, 2871, 2948. 1H NMR, : 1.31—1.80 (m, 20 H,
10 CH2); 1.99—2.12 (m, 8 H, 4 CH2CH=C); 3.28—3.80 (m, 8 H,
4 CH2—O); 4.52 (t, 2 H, 2 O—CH—O, J = 3.6 Hz); 5.33 (t, 2 H,
2 HC=CD, J = 7 Hz). 13C NMR, : 19.54 (C(17), C(22)); 25.49
(C(18), C(23)); 26.30 (C(3), C(12)); 26.01 (C(7), C(8)); 27.30
(C(4), C(11)); 29.30 (C(2), C(13)); 30.72 (C(16), C(21)); 62.09
(C(19), C(24)); 67.36 (C(1), C(14)); 98.65 (C(15), C(20)); 129.05
(t, C(6), C(9), JC,D = 23.5 Hz); 129.91 (C(5), C(10)).
2,2´ꢀ[Octadecaꢀ7Z,11Zꢀdienꢀ1,18ꢀdiylbis(oxy)]bistetrahydroꢀ
20
2Hꢀpyran (3d). The yield was 84%, nD 1.4949, Rf = 0.53.
Found (%): C, 74.28; H, 11.02. Calculated (%): C, 74.62; H, 11.18.
MS MALDI TOF: found m/z 450.7. C28H50O4. Calculated:
M = 450.7. IR, /cm–1: 815, 844, 869, 905, 968, 1034, 1077, 1122,
1136, 1183, 1200, 1259, 1275, 1283, 1322, 1352, 1384, 1440, 1464,
2ꢀ[(5ꢀCyclononꢀ2ꢀenꢀ1ꢀylpentꢀ3Zꢀenꢀ1ꢀyl)oxy]tetrahydroꢀ
2Hꢀpyran (7a). The yield was 81%, nD 1.4921, Rf = 0.49.
20
Found (%): C, 77.93; H, 10.92. Calculated (%): C, 78.03;
H, 11.03. MS MALDI TOF: found m/z 292.5. C19H32O2. Calꢀ
culated: M = 292.5. IR, /cm–1: 740, 871, 905, 981, 1030, 1073,
1125, 1201, 1351, 1448, 2864, 2929, 3001. 1H NMR, : 1.19—1.72
(m, 16 H, 8 CH2); 2.00—2.20 (m, 4 H, 2 CH2CH=); 2.47—2.57
(m, 1 H, CHCH2); 2.94—3.03 (m, 2 H, CH2CH=); 3.33—3.87
(m, 4 H, 2 CH2—O); 4.57 (t, 1 H, O—CH—O, J = 3.6 Hz);
5.02—5.14 (m, 1 H, CH=); 5.33—5.54 (m, 3 H, 3 CH=).
13C NMR, : 19.52 (C(17)); 24.53 (C(10)); 25.48 (C(18)); 25.97
(C(11)); 26.02 (C(9)); 26.48 (C(13)); 26.77 (C(12)); 28.13 (C(2));
30.73 (C(16)); 33.50 (C(5)); 34.84 (C(14)); 37.14 (C(6)); 62.09
(C(19)); 66.97 (C(1)); 98.59 (C(15)); 126.17 (C(3)); 129.45
(C(8)); 130.29 (C(4)); 134.90 (C(7)).
1
2855, 2937, 3005. H NMR, : 1.25—1.31 (m, 4 H, 2 CH2);
1.48—1.58 (m, 12 H, 6 CH2); 1.64—1.84 (m, 12 H, 6 CH2);
1.98—2.04 (m, 8 H, 4 CH2CH=C); 3.31—3.76 (m, 8 H, 4 CH2—O);
4.55 (t, 2 H, 2 O—CH—O, J = 4 Hz); 5.29—5.38 (m, 4 H,
4 HC=). 13C NMR, : 19.63 (C(21), C(26)); 25.53 (C(22), C(27));
26.17 (C(3), C(16)); 27.15 (C(6), C(13)); 27.37 (C(9), C(10));
29.16 (C(4), C(15)); 29.72 (C(2), C(17)); 30.60 (C(20), C(25));
30.70 (C(5), C(14)); 62.19 (C(23), C(28)); 67.55 (C(1), C(18));
98.73 (C(19), C(24)); 129.15 (C(8), C(11)); 130.17 (C(7), C(12)).
2,2´ꢀ[4,7ꢀDideuterooctadecaꢀ7Z,11Zꢀdienꢀ1,18ꢀdiylbis(oxy)]ꢀ
bistetrahydroꢀ2Hꢀpyran (4d). The yield was 82%, Rf = 0.53.
Found (%): C, 74.08; H + D, 11.14. C28H48D2O4. Calculatꢀ
ed (%): C, 74.29; H, 10.69; D, 0.89. MS (EI), m/z: 452 [M]+.
2ꢀ{4ꢀDeuteroꢀ[5ꢀ(2ꢀdeuterocyclononꢀ2ꢀenꢀ1ꢀyl)pentꢀ3Zꢀenꢀ
1ꢀyl]oxy}tetrahydroꢀ2Hꢀpyran (8a). The yield was 80%, Rf = 0.49.

TiꢀCatalyzed cyclomagnesiation of allenes
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 10, October, 2012
1947
Found (%): C, 77.23; H + D, 11.45. C19H30D2O2. Calculatꢀ
ed (%): C, 77.50; H, 10.27; D, 1.37. MS (EI), m/z: 294 [M]+.
IR, /cm–1: 740, 870, 905, 981, 1030, 1073, 1124, 1201, 1352,
2ꢀ(4,7ꢀDideuterotetradecaꢀ3Z,7Zꢀdienꢀ1ꢀyloxy)tetrahydroꢀ
2Hꢀpyran (12a). The yield was 81%, Rf = 0.45. Found (%):
C, 76.77; H + D, 12.08. C19H32D2O2. Calculated (%): C, 76.97;
H, 10.88; D, 1.36. MS (EI), m/z: 296 [M]+. IR, /cm–1: 815,
869, 905, 985, 1033, 1136, 1200, 1260, 1365, 1380, 1455, 1730,
1
1448, 2175 (C—D), 2864, 2929, 3002. H NMR, : 1.18—1.70
(m, 16 H, 8 CH2); 1.98—2.22 (m, 4 H, 2 CH2CH=); 2.47—2.56
(m, 1 H, CHCH2); 2.92—3.02 (m, 2 H, CH2CH=); 3.30—3.88
(m, 4 H, 2 CH2—O); 4.58 (t, 1 H, O—CH—O, J = 3.6 Hz); 5.08
(t, 1 H, CH=CD, J = 7 Hz); 5.42 (t, 1 H, CH=CD, J = 6.8 Hz).
13C NMR, : 19.53 (C(17)); 24.52 (C(10)); 25.47 (C(18)); 25.97
(C(11)); 26.04 (C(9)); 26.48 (C(13)); 26.78 (C(12)); 28.13 (C(2));
30.75 (C(16)); 33.51 (C(5)); 34.84 (C(14)); 37.16 (C(6)); 62.08
(C(19)); 66.98 (C(1)); 98.57 (C(15)); 126.16 (C(3)); 129.48 (C(8));
129.99 (t, C(4), JC,D = 23.5 Hz); 134.58 (t, C(7), JC,D = 23.0 Hz).
3ꢀ[5ꢀ(Benzyloxy)pentꢀ2Zꢀenꢀ1ꢀyl]cyclononene (7b). The
1
2165 (C—D), 2856, 2927, 3006. H NMR, : 0.90 (t, 3 H, Me,
J = 6.8 Hz); 1.26—1.32 (m, 8 H, 4 CH2); 1.49—1.84 (m, 6 H,
3 CH2); 1.94—2.12 (m, 8 H, 4 CH2CH=); 3.36—3.86 (m, 8 H,
4 CH2—O); 4.58 (t, 1 H, O—CH—O, J = 3.6 Hz); 5.39 (t, 1 H,
HC=CD, J = 7 Hz); 5.41 (t, 1 H, HC=CD, J = 7 Hz). 13C NMR,
: 14.05 (C(14)); 19.54 (C(17)); 22.64 (C(13)); 25.49 (C(18));
27.28 (C(5), C(6)); 27.46 (C(2)); 27.98 (C(9)); 28.95 (C(10));
29.68 (C(11)); 30.68 (C(16)); 31.78 (C(12)); 62.13 (C(19)); 67.01
(C(1)); 98.64 (C(15)); 125.98 (C(3)); 128.64 (t, C(7), JC,D
= 23.5 Hz); 130.34 (t, C(4), JC,D = 23.0 Hz); 131.21 (C(8)).
=
20
yield was 85%, nD 1.5141, Rf = 0.47. Found (%): C, 84.26;
H, 10.05. C21H30O. Calculated (%): C, 84.51; H, 10.13. MS,
m/z (Irel (%)): 298 [M]+ (1), 81 (100), 67 (39), 105 (31), 55 (26),
77 (22), 69 (18), 91 (17), 82 (15), 123 (14), 53 (11), 39 (10). IR,
/cm–1: 697, 736, 1028, 1101, 1361, 1495, 2855, 2926, 3003.
1H NMR, : 1.52 (m, 2 H, CH2); 1.67—1.79 (m, 8 H, 4 CH2);
2.12—2.29 (m, 2 H, CH2); 2.44—2.49 (m, 2 H, CH2); 2.61 (m, 1 H,
CH—CH2); 3.57 (t, 2 H, CH2—O, J = 7.2 Hz); 4.59 (s, 2 H,
O—CH2—Ph); 5.22—5.25 (m, 1 H, CH=); 5.48—5.55 (m, 2 H,
2 CH=); 5.59—5.63 (m, 1 H, =CH); 7.34—7.41 (m, 5 H, Ph).
13C NMR, : 24.64 (C(1)); 26.09 (C(10)); 26.14 (C(11)); 26.62
(C(12)); 26.87 (C(5)); 28.27 (C(2)); 33.63 (C(9)); 34.96 (C(14));
37.26 (C(6)); 70.04 (C(1)); 72.92 (C(15)); 126.20 (C(19)); 127.54
(C(18), C(20)); 127.65 (C(17), C(21)); 128.39 (C(8)); 129.63
(C(4)); 130.51 (C(3)); 135.00 (C(7)); 138.63 (C(16)).
2ꢀDeuteroꢀ3ꢀ[5ꢀ(benzyloxy)ꢀ2ꢀdeuteropentꢀ2Zꢀenꢀ1ꢀyl]ꢀ
cyclononene (8b). The yield was 87%, Rf = 0.47. Found (%):
C, 83.76; H + D, 10.52. C21H28D2O. Calculated (%): C, 83.94;
H, 9.39; D, 1.34. MS (EI), m/z: 300 [M]+. IR, /cm–1: 697, 735,
1028, 1101, 1361, 1496, 2180 (C—D), 2855, 2926, 3004. 1H NMR,
: 1.49—1.57 (m, 2 H, CH2); 1.66—1.77 (m, 8 H, 4 CH2);
2.12—2.26 (m, 2 H, CH2); 2.44—2.46 (m, 2 H, CH2); 2.63
(m, 1 H, CH—CH2); 3.58 (t, 2 H, CH2—O, J = 7.2 Hz); 4.58
(s, 2 H, O—CH2—Ph); 5.23 (t, 1 H, HC=CD, J = 7 Hz); 5.52
(t, 1 H, HC=CD, J = 7 Hz); 7.32—7.40 (m, 5 H, Ph). 13C NMR,
: 24.63 (C(1)); 26.08 (C(10)); 26.14 (C(11)); 26.64 (C(12));
26.88 (C(5)); 28.27 (C(2)); 33.62 (C(9)); 34.96 (C(14)); 37.27
(C(6)); 70.04 (C(1)); 72.93 (C(15)); 126.22 (C(19)); 127.55
(C(18), C(20)); 127.65 (C(17), C(21)); 128.36 (C(8)); 129.31
[(Tetradecaꢀ3Z,7Zꢀdienꢀ1ꢀyloxy)methyl]benzene (11b). The
yield was 88%, nD 1.5102, Rf = 0.46. Found (%): C, 83.72;
20
H, 10.51. C21H32O. Calculated (%): C, 83.94; H, 10.73. MS,
m/z (Irel (%)): 300 [M]+ (2), 105 (100), 123 (83), 77 (44), 70 (21),
122 (20), 55 (13), 51 (11), 106 (10). IR, /cm–1: 697, 735, 1028,
1
1101, 1361, 1495, 2855, 2926, 3007. H NMR, : 0.95 (t, 3 H,
Me, J = 8 Hz); 1.21—1.50 (m, 8 H, 4 CH2); 2.11—2.47 (m, 8 H,
4 CH2CH=C); 3.56 (t, 2 H, CH2—O, J = 8 Hz); 4.60 (s, 2 H,
CH2—Ph); 5.45—5.55 (m, 4 H, 4 HC=); 7.28—7.42 (m, 5 H,
Ph). 13C NMR, : 14.11 (C(14)); 22.74 (C(13)); 27.34 (C(5),
C(6)); 27.59 (C(9)); 28.09 (C(2)); 29.07 (C(10)); 29.78 (C(11));
31.87 (C(12)); 70.06 (C(1)); 72.92 (C(15)); 125.98 (C(19));
127.53 (C(3)); 127.68 (C(17), C(21)); 128.38 (C(18), C(20));
129.01 (C(7)); 130.54 (C(4)); 131.35 (C(8)); 138.61 (C(16)).
[(4,7ꢀDideuterotetradecaꢀ3Z,7Zꢀdienꢀ1ꢀyloxy)methyl]benzꢀ
ene (12b). The yield was 87%, Rf = 0.46. Found (%): C, 83.15;
H + D, 11.12. C12H30D2O. Calculated (%): C, 83.38; H, 10.00;
D, 1.33. MS (EI), m/z: 302 [M]+. IR, /cm–1: 696, 735, 1028,
1
1101, 1361, 1495, 2170 (C—D), 2856, 2926, 3007. H NMR,
: 0.94 (t, 3 H, Me, J = 8 Hz); 1.21—1.52 (m, 8 H, 4 CH2);
2.12—2.46 (m, 8 H, 4 CH2CH=C); 3.58 (t, 2 H, CH2—O, J = 8 Hz);
4.62 (s, 2 H, CH2Ph); 5.47 (t, 1 H, HC=CD, J = 7 Hz); 5.52
(t, 1 H, HC=CD, J = 7 Hz); 7.28—7.44 (m, 5 H, Ph). 13C NMR,
: 14.09 (C(14)); 22.72 (C(13)); 27.36 (C(5), C(6)); 27.58 (C(9));
28.06 (C(2)); 29.07 (C(10)); 29.76 (C(11)); 31.88 (C(12));
70.04 (C(1)); 72.91 (C(15)); 125.96 (C(19)); 127.52 (C(3));
127.65 (C(17), C(21)); 128.36 (C(18), C(20)); 128.75 (t, C(7),
JC,D = 23.5 Hz); 130.24 (t, C(4), JC,D = 24.0 Hz); 131.3 (C(8));
138.62 (C(16)).
(t, C(4), JC,D = 23.5 Hz); 130.52 (C(3)); 134.79 (t, C(7), JC,D
=
= 23.5 Hz); 138.62 (C(16)).
2ꢀ[(9ꢀPhenylnonaꢀ3Z,7Zꢀdienꢀ1ꢀyl)oxy]tetrahydroꢀ2Hꢀpyrꢀ
an (11c). The yield was 84%, nD20 1.5311, Rf = 0.44. Found (%):
C, 79.79; H, 10.43. C20H28O2. Calculated (%): C, 79.96;
H, 10.65. MS, m/z (Irel (%)): 300 [M]+ (2), 85 (100), 91 (80),
105 (43), 104 (37), 101 (24), 131 (21), 84 (19), 92 (18), 41 (17),
57 (15), 43 (14), 56 (13), 67 (12), 117 (11). IR, /cm–1: 699,
747, 812, 869, 905, 983, 1032, 1075, 1120, 1200, 1261,
2ꢀ(Tetradecaꢀ3Z,7Zꢀdienꢀ1ꢀyloxy)tetrahydroꢀ2Hꢀpyran (11a).
The yield was 81%, nD20 1.4695, Rf = 0.45. Found (%): C, 77.36;
H, 11.22. C19H34O2. Calculated (%): C, 77.50; H, 11.64. MS,
m/z (Irel (%)): 294 [M]+ (2), 85 (100), 55 (48), 105 (46), 43 (41),
57 (35), 41 (30), 207 (27), 101 (25), 131 (24), 69 (23), 77 (21),
167 (18), 73 (15), 129 (14), 70 (12). IR, /cm–1: 814, 869, 905,
985, 1033, 1137, 1200, 1260, 1364, 1380, 1455, 1730, 2856, 2927,
1
1352, 1453, 1762, 2870, 2938, 3390. H NMR, : 1.57—1.91
1
3007. H NMR, : 0.89 (t, 3 H, Me, J = 6.4 Hz); 1.27—1.30
(m, 6 H, 3 CH2); 2.24—2.47 (m, 6 H, 3 CH2CH=); 3.46 (d, 2 H,
CH2Ph, J = 6.4 Hz); 3.53—3.96 (m, 4 H, 2 CH2—O); 4.67
(t, 1 H, O—CH—O, J = 3.6 Hz); 5.50—5.72 (m, 4 H, 4 HC=);
7.24—7.35 (m, 5 H, Ph). 13C NMR, : 19.63 (C(18)); 25.59
(C(19)); 27.40, 27.48 (C(5), C(6)); 28.07 (C(2)); 30.78 (C(17));
33.61 (C(9)); 62.17 (C(20)); 67.06 (C(1)); 98.70 (C(16));
125.92 (C(13)); 126.13 (C(3)); 128.38 (C(12), C(14)); 128.43
(C(11), C(15)); 128.62 (C(8)); 130.14 (C(7)); 131.02 (C(4));
141.08 (C(10)).
(m, 8 H, 4 CH2); 1.49—1.86 (m, 6 H, 3 CH2); 1.94—2.13 (m, 8 H,
4 CH2CH=); 3.38—3.87 (m, 8 H, 4 CH2—O); 4.59 (t, 1 H,
O—CH—O, J = 3.6 Hz); 5.35—5.46 (m, 4 H, 4 HC=). 13C NMR,
: 14.06 (C(14)); 19.54 (C(17)); 22.63 (C(13)); 25.49 (C(18));
27.25 (C(5), C(6)); 27.48 (C(2)); 27.98 (C(9)); 28.97 (C(10));
29.68 (C(11)); 30.69 (C(16)); 31.77 (C(12)); 62.15 (C(19)); 67.02
(C(1)); 98.64 (C(15)); 125.97 (C(3)); 128.94 (C(7)); 130.41
(C(4)); 131.20 (C(8)).

1948
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 10, October, 2012
D´yakonov et al.
2ꢀ[(3,6ꢀDideuteroꢀ9ꢀphenylnonaꢀ3Z,7Zꢀdienꢀ1ꢀyl)oxy]tetraꢀ
hydroꢀ2Hꢀpyran (12c). The yield was 83%, Rf = 0.44. Found (%):
C, 79.28; H + D, 9.63. C20H26D2O2. Calculated (%): C, 79.42;
H, 8.66; D, 1.33. MS (EI), m/z: 302 [M]+. IR, /cm–1: 698, 747,
812, 869, 906, 983, 1032, 1074, 1120, 1200, 1261, 1352, 1452,
2ꢀ(6,9ꢀDideuterotetradecaꢀ5Z,9Zꢀdienꢀ1ꢀyloxy)tetrahydroꢀ
2Hꢀpyran (12e). The yield was 84%, Rf = 0.39. Found (%):
C, 76.68; H + D, 12.11. C19H32D2O2. Calculated (%): C, 76.97;
H, 10.88; D, 1.36. MS (EI), m/z: 296 [M]+. IR, /cm–1: 814,
868, 905, 970, 992, 1033, 1078, 1121, 1137, 1159, 1182, 1200,
1
1
1762, 2175 (C—D), 2870, 2939, 3390. H NMR, : 1.56—1.90
1354, 1380, 1440, 2165 (C—D), 2853, 2924, 3005. H NMR,
(m, 6 H, 3 CH2); 2.24—2.48 (m, 6 H, 3 CH2CH=); 3.45 (d, 2 H,
CH2Ph, J = 6.4 Hz); 3.52—3.96 (m, 4 H, 2 CH2—O); 4.68 (t, 1 H,
O—CH—O, J = 3.6 Hz); 5.50—5.72 (m, 2 H, 2 HC=CD);
7.26—7.34 (m, 5 H, Ph). 13C NMR, : 19.62 (C(18)); 25.59
(C(19)); 27.41, 27.47 (C(5), C(6)); 28.08 (C(2)); 30.76 (C(17));
33.61 (C(9)); 62.18 (C(20)); 67.06 (C(1)); 98.72 (C(16)); 125.90
(C(13)); 126.15 (C(3)); 128.37 (C(12), C(14)); 128.43 (C(11),
C(15)); 128.60 (C(8)); 129.87 (t, C(7), JC,D = 24.5 Hz); 130.72
(t, C(4), JC,D = 24 Hz); 141.08 (C(10)).
: 0.91 (t, 3 H, Me, J = 6.8 Hz); 1.27—1.35 (m, 14 H, 7 CH2);
2.02—2.08 (m, 8 H, 4 CH2CH=); 3.40—3.87 (m, 4 H, 2 CH2—O);
4.57 (t, 1 H, O—CH—O, J = 3.6 Hz); 5.37 (t, 1 H, HC=CD,
J = 7 Hz); 5.42 (t, 1 H, HC=CD, J = 7 Hz). 13C NMR, : 14.01
(C(14)); 19.64 (C(17)); 22.33 (C(13)); 25.54 (C(18)); 26.39
(C(3)); 27.01 (C(4)); 27.05 (C(2)); 27.38 (C(7)); 27.44 (C(8));
29.46 (C(11)); 30.76 (C(12)); 31.92 (C(16)); 62.16 (C(19)); 67.44
(C(1)); 98.77 (C(15)); 128.84 (t, C(9), JC,D = 24.0 Hz); 129.31
(t, C(6), JC,D = 23.5 Hz); 129.84 (C(5)); 129.90 (C(10)).
2ꢀ(Eucosaꢀ4Z,8Zꢀdienꢀ1ꢀyloxy)tetrahydroꢀ2Hꢀpyran (11d).
The yield was 87%, nD20 1.4801, Rf = 0.42. Found (%): C, 79.18;
H, 12.69. Calculated (%): C, 79.35; H, 12.82. MS MALDI TOF:
2ꢀ(Hexadecaꢀ5Z,9Zꢀdienꢀ1ꢀyloxy)tetrahydroꢀ2Hꢀpyran (11f).
The yield was 89%, nD20 1.4831, Rf = 0.41. Found (%): C, 78.41;
H, 11.69. Calculated (%): C, 78.20; H, 11.88. MS MALDI TOF:
found m/z 322.5. C21H38O2. Calculated: M = 322.5. IR, /cm–1
:
found m/z 392.6. C26H48O2. Calculated: M = 392.6. IR, /cm–1
:
721, 905, 971, 992, 1034, 1078, 1121, 1137, 1159, 1182, 1200,
1260, 1380, 1401, 1441, 2853, 2924, 3005. 1H NMR, : 0.89 (t, 3 H,
Me, J = 6.7 Hz); 1.19—1.39 (m, 22 H, 11 CH2); 1.50—1.68
(m, 6 H, 3 CH2); 2.00—2.15 (m, 8 H, 4 CH2CH=C); 3.38—3.87
(m, 4 H, 2 CH2—O); 4.58 (t, 1 H, O—CH—O, J = 4 Hz); 5.36—5.41
(m, 4 H, 4 HC=). 13C NMR, : 14.08 (C(21)); 19.62 (C(24));
22.69 (C(20)); 23.91 (C(3)); 25.53 (C(25)); 27.26 (C(10)); 27.33
(C(6)); 27.37 (C(7)); 29.37 (C(2)); 29.50, 29.63, 29.74, 29.83
(C(11), C(12), C(13), C(14)); 29.67, 29.70 (2 C, C(15), C(16),
C(17), C(18)); 30.76 (C(23)); 31.93 (C(19)); 62.17 (C(26)); 66.93
(C(1)); 98.77 (C(22)); 129.02 (C(9)); 129.42 (C(4)); 129.76
(C(8)); 130.37 (C(5)).
815, 869, 905, 971, 992, 1034, 1078, 1121, 1137, 1159, 1182,
1200, 1353, 1380, 1441, 2853, 2924, 3005. 1H NMR, : 0.87 (t, 3 H,
Me, J = 7.2 Hz); 1.26—1.85 (m, 18 H, 9 CH2); 2.00—2.07
(m, 8 H, 4 CH2CH=); 3.38—3.87 (m, 4 H, 2 CH2—O); 4.56
(t, 1 H, O—CH—O, J = 3.2 Hz); 5.34—5.38 (m, 4 H, 4 HC=).
13C NMR, : 14.04 (C(16)); 19.62 (C(19)); 22.63 (C(15)); 25.52
(C(20)); 26.38 (C(3)); 27.03 (C(4)); 27.23 (C(2)); 27.36 (C(7));
27.40 (C(8)); 28.96 (C(11)); 29.36 (C(12)); 29.72 (C(13));
30.73 (C(18)); 31.77 (C(14)); 62.13 (C(21)); 67.37 (C(1));
98.68 (C(17)); 129.03 (C(9)); 129.42 (C(6)); 129.88 (C(5));
130.30 (C(10)).
2ꢀ(6,9ꢀDideuterohexadecaꢀ5Z,9Zꢀdienꢀ1ꢀyloxy)tetrahydroꢀ
2Hꢀpyran (12f). The yield was 88%, Rf = 0.41. Found (%): C, 77.68;
H + D, 12.28. Calculated (%): C, 77.72; H, 11.18; D, 1.24. MS
MALDI TOF: found m/z 324.5. C21H36D2O2. Calculated:
M = 324.5. IR, /cm–1: 816, 869, 905, 971, 992, 1034, 1078,
1121, 1136, 1159, 1182, 1200, 1353, 1380, 1441, 2175 (C—D),
2ꢀ(5,8ꢀDideuteroeucosaꢀ4Z,8Zꢀdienꢀ1ꢀyloxy)tetrahydroꢀ2Hꢀ
pyran (12d). The yield was 87%, Rf = 0.42. Found (%): C, 78.74;
H + D, 13.09. C26H47D2O2. Calculated (%): C, 78.96; H, 12.27;
D, 0.98. MS (EI), m/z: 394 [M]+. IR, /cm–1: 721, 905, 970,
992, 1034, 1078, 1121, 1137, 1159, 1181, 1200, 1260, 1380, 1401,
1440, 2160 (C—D), 2853, 2924, 3005. 1H NMR, : 0.89 (t, 3 H,
Me, J = 6.7 Hz); 1.19—1.38 (m, 22 H, 11 CH2); 1.50—1.68
(m, 6 H, 3 CH2); 2.00—2.20 (m, 8 H, 4 CH2CH=C); 3.38—3.88
(m, 4 H, 2 CH2—O); 4.57 (t, 1 H, O—CH—O, J = 4 Hz); 5.50—5.58
(m, 2 H, 2 HC=CD). 13C NMR, : 14.05 (C(21)); 19.64 (C(24));
22.68 (C(20)); 23.91 (C(3)); 25.55 (C(25)); 27.26 (C(10)); 27.34
(C(6)); 27.37 (C(7)); 29.38 (C(2)); 29.51, 29.63, 29.75, 29.84
(C(11), C(12), C(13), C(14)); 29.67, 29.71 (2 C, C(15), C(16),
C(17), C(18)); 30.78 (C(23)); 31.94 (C(19)); 62.18 (C(26)); 66.94
(C(1)); 98.78 (C(22)); 129.04 (C(9)); 129.41 (C(4)); 129.48
(t, C(8), JC,D = 23.5 Hz); 130.07 (t, C(5), JC,D = 24 Hz).
2ꢀ(Tetradecaꢀ5Z,9Zꢀdienꢀ1ꢀyloxy)tetrahydroꢀ2Hꢀpyran (11e).
The yield was 84%, nD20 1.4814, Rf = 0.39. Found (%): C, 77.39;
H, 11.48. Calculated (%): C, 77.50; H, 11.64. MS MALDI TOF:
1
2853, 2924, 3005. H NMR, : 0.88 (t, 3 H, Me, J = 7.0 Hz);
1.26—1.88 (m, 18 H, 9 CH2); 2.00—2.12 (m, 8 H, 4 CH2CH=);
3.38—3.85 (m, 4 H, 2 CH2—O); 4.57 (t, 1 H, O—CH—O,
J = 3.2 Hz); 5.34—5.37 (m, 2 H, 2 HC=CD). 13C NMR, : 14.02
(C(16)); 19.64 (C(19)); 22.61 (C(15)); 25.50 (C(20)); 26.38
(C(3)); 27.04 (C(4)); 27.23 (C(2)); 27.36 (C(7)); 27.42 (C(8));
28.96 (C(11)); 29.35 (C(12)); 29.71 (C(13)); 30.73 (C(18)); 31.78
(C(14)); 62.14 (C(21)); 67.37 (C(1)); 98.67 (C(17)); 128.75
(t, C(9), JC,D = 24.0 Hz); 129.12 (t, C(6), JC,D = 24.0 Hz);
129.87 (C(5)); 130.31 (C(10)).
2ꢀ(Hexadecaꢀ7Z,11Zꢀdienꢀ1ꢀyloxy)tetrahydroꢀ2Hꢀpyran
20
(11g). The yield was 94%, nD 1.4841, Rf = 0.38. Found (%):
C, 78.08; H, 11.64. Calculated (%): C, 78.20; H, 11.88. MS
MALDI TOF: found m/z 322.5. C21H38O2. Calculated: M = 322.5.
IR, /cm–1: 814, 869, 905, 971, 990, 1034, 1078, 1121, 1136,
1159, 1182, 1200, 1353, 1380, 1441, 2853, 2925, 3005. 1H NMR,
: 0.88 (t, 3 H, Me, J = 5.2 Hz); 1.26—1.33 (m, 12 H, 6 CH2);
1.50—1.65 (m, 6 H, 3 CH2); 2.02—2.16 (m, 8 H, 4 CH2CH=);
3.38—3.88 (m, 4 H, 2 CH2—O); 4.57 (t, 1 H, O—CH—O, J = 4 Hz);
5.35—5.40 (m, 4 H, 4 HC=). 13C NMR, : 13.96 (C(16)); 19.64
(C(19)); 22.45 (C(15)); 25.52 (C(20)); 26.20 (C(3)); 26.93 (C(6));
27.18 (C(13)); 27.39 (C(9), C(10)); 29.13 (C(14)); 29.66 (C(4));
29.72 (C(2)); 30.80 (C(18)); 31.96 (C(5)); 62.19 (C(21)); 67.57
(C(1)); 98.75 (C(17)); 129.05 (C(11)); 129.63 (C(7)); 130.17
(C(12)); 130.60 (C(8)).
found m/z 294.5. C19H34O2. Calculated: M = 294.5. IR, /cm–1
:
814, 869, 905, 970, 992, 1034, 1078, 1121, 1137, 1159, 1182,
1200, 1354, 1380, 1441, 2853, 2924, 3005. 1H NMR, : 0.90 (t, 3 H,
Me, J = 6.8 Hz); 1.27—1.33 (m, 14 H, 7 CH2); 2.03—2.07
(m, 8 H, 4 CH2CH=); 3.40—3.89 (m, 4 H, 2 CH2—O); 4.58 (t, 1 H,
O—CH—O, J = 3.6 Hz); 5.36—5.41 (m, 4 H, 4 HC=). 13C NMR,
: 13.97 (C(14)); 19.62 (C(17)); 22.32 (C(13)); 25.52 (C(18));
26.39 (C(3)); 27.00 (C(4)); 27.05 (C(2)); 27.37 (C(7)); 27.42
(C(8)); 29.46 (C(11)); 30.75 (C(12)); 31.92 (C(16)); 62.18
(C(19)); 67.43 (C(1)); 98.75 (C(15)); 129.07 (C(9)); 129.61
(C(6)); 129.82 (C(5)); 129.92 (C(10)).

TiꢀCatalyzed cyclomagnesiation of allenes
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 10, October, 2012
1949
2ꢀ(8,11ꢀDideuterohexadecaꢀ7Z,11Zꢀdienꢀ1ꢀyloxy)tetrahydroꢀ
2Hꢀpyran (12g). The yield was 92%, Rf = 0.38. Found (%):
C, 77.61; H + D, 12.24. Calculated (%): C, 77.72; H, 11.18;
D, 1.24. MS MALDI TOF: found m/z 324.5. C21H36D2O2. Calꢀ
culated: M = 324.5. IR, /cm–1: 815, 869, 905, 971, 990, 1034,
1078, 1121, 1136, 1159, 1183, 1200, 1353, 1380, 1441, 2160 (C—D),
7. V. N. Odinokov, E. P. Serebryakov, Sintez feromonov naseꢀ
komykh [Synthesis of Insects´ Feromones], Gilem, Ufa, 2001,
372 pp. (in Russian).
8. K. Bauer, D. Garbe, H. Surburg, Common Fragrance and
Flavor Materials: Preparation, Properties and Uses, John Wiley
and Sons, Weinheim (Germany), 1997, 290 pp.
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Chem., 2008, 4, № 48; doi:10.3762/bjoc.4.48.
10. AttaꢀurꢀRahman, Studies in Natural Products Chemistry,
V. 26, Bioactive Natural Products (Part G), Amsderdam,
2002, p. 63.
11. G. Levy, G. Nelson, Carbonꢀ13 Nuclear Magnetic Resonance
for Organic Chemists, Wiley, New York, 1972, 292 pp.
12. A. J. Gordon, R. A. Ford, The Chemist’s Companion, J. Wilꢀ
ley and Sons, New York—London—Sydney—Toronto, 1972,
300 pp.
1
2853, 2925, 3005. H NMR, : 0.89 (t, 3 H, Me, J = 6.2 Hz);
1.26—1.34 (m, 12 H, 6 CH2); 1.51—1.63 (m, 6 H, 3 CH2);
2.02—2.14 (m, 8 H, 4 CH2CH=); 3.38—3.86 (m, 4 H, 2 CH2—O);
4.58 (t, 1 H, O—CH—O, J = 4 Hz); 5.36 (t, 1 H, HC=CD,
J = 7 Hz); 5.39 (t, 1 H, HC=CD, J = 7 Hz). 13C NMR, : 13.98
(C(16)); 19.62 (C(19)); 22.45 (C(15)); 25.54 (C(20)); 26.21
(C(3)); 26.94 (C(6)); 27.19 (C(13)); 27.38 (C(9), C(10)); 29.14
(C(14)); 29.68 (C(4)); 29.72 (C(2)); 30.81 (C(18)); 31.98 (C(5));
62.18 (C(21)); 67.57 (C(1)); 98.76 (C(17)); 128.83 (t, C(11)
JC,D = 24.5 Hz); 129.62 (C(7)); 130.18 (C(12)); 130.32 (t, C(8),
JC,D = 24.0 Hz).
13. U. M. Dzhemilev, V. A. D´yakonov, L. O. Khafisova, A. G.
Ibragimov, Zh. Org. Khim., 2005, 41, 363 [Russ. J. Org. Chem.
(Engl. Transl.), 2005, 41, 352].
14. Pat. US 4609498, 1986; RZhKhim. [Russ. Ref. J. Chem.],
1987, 60446P (in Russian).
This work was financially supported by the Russian
Foundation for Basic Research (Project Nos 10ꢀ03ꢀ00046,
11ꢀ03ꢀ00103, and 11ꢀ03ꢀ97001).
15. S. T. Ioffe, A. N. Nesmeyanov, Metody elementoorganicheskoi
khimii. Podgruppa magniya, berilliya, kal´tsiya, strontsiya,
bariya [Methods of Organoelement Chemistry. The Subgroup of
Magnesium, Beryllium, Calcium, Strontium, Barium], AN
SSSR, Moscow, 1963, 561 pp. (in Rusian).
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Received April 17, 2012;
in revised form July 4, 2012