C O M M U N I C A T I O N S
Scheme 3
Scheme 5
Scheme 4
of the 1,4,12-triene 23 with 8 furnished the Z-configured 11-
membered lactone 25 in 81% yield.
In summary, we have developed a highly flexible asymmetric
synthesis of functionalized medium-sized carbocycles and lactones
through RCM of sulfoximine-substituted trienes. Because of the
alkenyl sulfoximine moiety8 of the carbocycles and lactones, further
transformations can be envisioned including a Michael addition8
followed by a Cl-substitution of the sulfoximine group,6b a Ni-
catalyzed cross-coupling reaction with organometal reagents9 and
a migratory Cl-substitution of the sulfoximine group.10
Acknowledgment. Financial support of this work by the
Deutsche Forschungsgemeinschaft (SFB 380) is gratefully acknowl-
edged. We thank Prof. S. Blechert for his collaboration in a study
of the RCM of sulfoximine-substituted dienes.
Supporting Information Available: Experimental procedures and
characterization data for 2a, 5a, 9, 17, 21, 23, and 25. This material is
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mol % of 8 in CH2Cl2 at reflux for 16 h furnished the eight-
membered carbocycle 17 in 90% yield. The S-configuration of 16
and 17 at C1 was tentatively assigned on the basis of model
considerations of the addition of the Grignard reagent to 15.
To demonstrate the synthetic potential of the sulfoximine-
substituted carbocycles, the 11-membered derivative 12 was treated
with AcOH/H2O in THF, which gave the allylic alcohol 18 in 96%
yield (Scheme 4). We ascribe the highly selective cleavage of the
tBuMe2Si group in the presence of the Et3Si group to a neighboring
effect exerted by the protonated sulfoximine group. Protonation of
sulfoximine 12 should give salt 12/AcOH in which the tBuMe2Si
group could be selectively activated toward a nucleophilic attack
by an intramolecular hydrogen bond. Oxidation of alcohol 18 with
DMP afforded enone 19 in 90%. An example for the facile
substitution of the sulfoximine group is provided by the cross-
coupling reaction of the alkenyl sulfoximine 9 with LiCuMe2 (3
equiv) in the presence of ClSiMe3, which gave the methylated
carbocycle 20 in 60% yield (95% based on recovered 9).
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substituted diene 3c was probed. The esterification of alcohol 21,
obtained by desilylation of 5c (HF/pyridine, THF, 95%), with
acrylic acid and pent-4-enoic acid by using DCC/DMAP afforded
ester 22 in 47% yield (80% yield based on recovered 21) and ester
23 in 67% yield (97% yield based on recovered 21), respectively
(Scheme 5). The treatment of the 1,4,10-triene 22 (0.005 M) with
8 mol % of 8 in toluene at reflux for 16 h gave the Z-configured
9-membered lactone 24 in 87% yield. The similar RCM reaction
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