Palladium(0)-Catalyzed Highly Regio- and
Stereoselective Addition of Organoboronic Acids
with 1,2-Allenylphosphonates Forming Tri- or
Tetrasubstituted 1(E)-Alkenylphosphonates
Shengming Ma,* Hao Guo, and Fei Yu
FIGURE 1. 1H-1H NOESY of E-3aa.
State Key Laboratory of Organometallic Chemistry, Shanghai
Institute of Organic Chemistry, Chinese Academy of Sciences,
354 Fenglin Lu, Shanghai 200032, P. R. China
or triple bonds are rare.9 Recently, Oh et al. reported the Pd-
catalyzed addition reaction of alkynes with organoboronic acids
affording trisubstituted alkenes stereoselectively.9 We and Oh
et al. reported the Pd-catalyzed reaction of allenes with
organoboronic acids in the presence of HOAc.10-12 However,
the regio- and stereoselectivity or yield is not excellent. On the
other hand, phosphonates show very important bioactivities,13
and 1-alkenylphosphonates are important intermediates in
organic synthesis,14 so highly stereoselective methods for the
synthesis of substituted 1-alkenylphosphonates are desirable.
Here, we wish to report a highly regio- and stereoselective
palladium(0)-catalyzed addition of organoboronic acids with 1,2-
allenyl phosphonates in the presence of HOAc forming tri- or
tetrasubstituted 1(E)-alkenyl phosphonates.
ReceiVed March 29, 2006
The solvent effect of the addition reaction of 1,2-allenyl
phosphonate 1a with phenylboronic acid 2a was studied first
(Table 1). In MeNO2, dioxane, ether, MeCN, and toluene, no
reaction was observed (entries 1-5, Table 1). In MeOH,
however, two regioisomeric products E-3aa and 4aa were
formed in 75% combined yield with a ratio of 85:15 (entry 6,
Table 1). The configuration of the CdC bond in 3aa was
A highly regio- and stereoselective palladium(0)-catalyzed
addition of organoboronic acids with 1,2-allenylphosphonates
in the presence of HOAc forming tri- or tetrasubstituted 1(E)-
alkenylphosphonates is reported in this paper. The stereo-
selectivity is much higher than the reported cases. The effects
of different R1, R2, and R3 were studied. A mechanism of
this reaction is proposed on the basis of our previous study.
1
determined by the H-1H NOESY spectrum (Figure 1). The
reaction in DMF and CH2Cl2 is highly regio- and stereoselective,
but the yield is rather poor (entries 7 and 8, Table 1). Best results
were obtained when the reaction was conducted in THF (entry
9, Table 1). Under this set of standard reaction conditions, the
reaction afforded E-3aa as the only product highly selectively
in good yield.
We also tried other palladium catalysts with some of the
typical results shown in Table 2. No better results were observed;
thus, Pd(PPh3)4 was chosen as the catalyst for this reaction.
The effects of the loading of Pd(PPh3)4 and the temperature
were then examined carefully (Table 3). The results indicated
Organoboronic acids are very important and useful reagents
in organic synthesis.1 One of the most notable reactions is their
palladium-catalyzed cross-coupling reaction with organic halides
(the Suzuki couple reaction).2 Another important application is
the rhodium- or nickel-catalyzed conjugate additions3 of orga-
noboronic acids to electron-deficient C-C double or triple
bonds,4-6 CdO bonds (aldehydes),7 and CdN bonds (N-
sulfonylimines).8 Transition metal-catalyzed addition reactions
of organoboronic acids to electron-rich carbon-carbon double
* To whom correspondence should be addressed. Fax: (+86) 21-64167510.
(1) (a) Organic Chemistry; Day, A. R., Joullie´, M. M., Eds.; Van
Nostrand: Princeton, 1960. (b) Topics in Current Chemistry; Armin, M.,
Ed.; Springer: Berlin, 2003.
(6) For some of the nickel-catalyzed reactions, see: (a) Shirakawa, E.;
Takahashi, G.; Tsuchimoto, T.; Kawakami, Y. Chem. Commun. 2001,
2688-2689. (b) Shirakawa, E.; Takahashi, G.; Tsuchimoto, T.; Kawakami,
Y. Chem. Commun. 2002, 2210-2211.
(7) (a) Ueda, M.; Miyaura, N. J. Org. Chem. 2000, 65, 4450-4452. (b)
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(12) For the mechanistic study, see: Qian, R.; Guo, H.; Liao, Y.; Guo,
Y.; Ma, S. Angew. Chem., Int. Ed. 2005, 44, 4771-4774.
(13) For some reviews, see: (a) Caruthers, M. H. Acc. Chem. Res. 1991,
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Hayashi, T.; Inoue, K.; Taniguchi, N.; Ogasawara, M. J. Am. Chem. Soc.
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10.1021/jo060672t CCC: $33.50 © 2006 American Chemical Society
Published on Web 07/19/2006
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J. Org. Chem. 2006, 71, 6634-6636