Organic Letters
Letter
Catalytic Activity toward Reactions of Propargylic Alcohols with
Aromatic Compounds. Organometallics 2008, 27, 4017−4020.
(b) Trost, B. M.; Livingston, R. C. Two-Metal Catalyst System for
Redox Isomerization of Propargyl Alcohols to Enals and Enones. J.
Am. Chem. Soc. 1995, 117, 9586−9587. (c) Ma, D.; Lu, X. A Simple
Route to α,β-Unsaturated Aldehydes from Prop-2-ynols. J. Chem. Soc.,
Chem. Commun. 1989, 890−891. Rh catalysis: (d) Tanaka, K.; Shoji,
T. Cationic Rhodium(I)/BINAP Complex-Catalyzed Isomerization of
Secondary Propargylic Alcohols to α,β-Enones. Org. Lett. 2005, 7,
3561−3563. (e) Saïah, M. K. E.; Pellicciari, R. Rhodium-Catalyzed
Redox Isomerization of Hydroxy Alkynes to trans Keto and Hydroxy
Vinyl Esters. A Short and Stereoselective Synthesis of Dipeptide
Isosters. Tetrahedron Lett. 1995, 36, 4497−4500. Ir catalysis: (f) Ma,
D.; Lu, X. Isomerization of Propargylic Alcohols Catalyzed by an
Iridium Complex. Tetrahedron Lett. 1989, 30, 2109−2112. Pd
catalysis: (g) Arcadi, A.; Cacchi, S.; Marinelli, F.; Misiti, D. The
Reaction of Alkyl 4-Hydroxy-2-alkynoates and 4-Hydroxy-2-alkyn-1-
ones with Palladium Tributylammonium Formate and with Tributyl-
amine: Preparation of 1,4-Dicarbonyl Compounds. Tetrahedron Lett.
1988, 29, 1457−1460.
(3) (a) Mizota, I.; Matsuda, Y.; Hachiya, I.; Shimizu, M. N-
Allylideneamines Derived from Acrolein: Synthesis and Use as
Acceptors of Two Nucleophiles. Eur. J. Org. Chem. 2009, 2009,
4073−4084. (b) Ben-Efraim, D. A. The Prototropic Rearrangement of
Secondary Propargylic Amines. Tetrahedron 1973, 29, 4111−4125.
(4) For reviews on allenylamides, see: (a) Lu, T.; Lu, Z.; Ma, Z.-X.;
Zhang, Y.; Hsung, R. P. Allenamides: A Powerful and Versatile
Building Block in Organic Synthesis. Chem. Rev. 2013, 113, 4862−
4904. (b) Wei, L.-l.; Xiong, H.; Hsung, R. P. The Emergence of
Allenamides in Organic Synthesis. Acc. Chem. Res. 2003, 36, 773−782.
(5) Liu, W.; Wang, H.; Zhao, H.; Li, B.; Chen, S. Y. (OTf)3-
Catalyzed Cascade Propargylic Substitution/Aza-Meyer-Schuster
Rearrangement: Stereoselective Synthesis of α,β-Unsaturated Hydra-
zones and Their Conversion into Pyrazoles. Synlett 2015, 26, 2170−
2174.
10057−10060. (f) Hori, S.; Murai, M.; Takai, K. Rhenium-Catalyzed
anti-Markovnikov Addition Reaction of Methanetricarboxylates to
Unactivated Terminal Acetylenes. J. Am. Chem. Soc. 2015, 137, 1452−
1457. (g) Xia, D.; Wang, Y.; Du, Z.; Zheng, Q.-Y.; Wang, C.
Rhenium-Catalyzed Regiodivergent Addition of Indoles to Terminal
Alkynes. Org. Lett. 2012, 14, 588−591. (h) S, S. Y.; Kuninobu, Y.;
Takai, K. Rhenium-Catalyzed Hydroamidation of Unactivated
Terminal Alkynes: Synthesis of (E)-Enamides. Org. Lett. 2007, 9,
5609−5611.
(10) Fan, W.; Yuan, W.; Ma, S. Unexpected E-Stereoselective
Reductive A3-Coupling Reaction of Terminal Alkynes with Aldehydes
and Amines. Nat. Commun. 2014, 5, 3884−3893.
(11) Wu, X.; Chen, S.-S.; Hu, Y.; Gong, L.-Z. Gold-Catalyzed [1,5]-
Hydride Shift onto Unactivated Alkynes to Trigger an Intermolecular
Diels−Alder Reaction. Org. Lett. 2014, 16, 3820−3823.
(12) For reviews on 1,5-hydrogen transfer mediated by transition
metals, see: (a) Haibach, M. C.; Seidel, D. C-H. Bond
Functionalization through Intramolecular Hydride Transfer. Angew.
Chem., Int. Ed. 2014, 53, 5010−5036. (b) Peng, B.; Maulide, N. The
Redox-Neutral Approach to C-H Functionalization. Chem. - Eur. J.
2013, 19, 13274−13287.
(13) A similar 1,5-shift of the hydrogen atom adjacent to the
nitrogen atom to the vinylidene α-carbon atom was proposed
́
previously; see: (a) Hyder, I.; Jimenez-Tenorio, M.; Puerta, M. C.;
Valerga, P. Nucleophilic Addition Reactions to Allenylidene
Complexes of Ruthenium Bearing Hemilabile P,N Ligands: Isolation
of the Vinylcarbene Complex [Cp*Ru
= CHCH =
CPh2(iPr2PNHPy)][PF6]. Organometallics 2011, 30, 726−737.
(b) Ipaktschi, J.; Mohsseni-Ala, J.; Dulmer, A.; Loschen, C.;
̈
Frenking, G. Reaction of Tungsten η1-Acetylide Complexes [(η5-
C5H5)(NO)(CO)W−C≡C−R]Li with Iminium Ions. Organometallics
2005, 24, 977−989.
(14) For other examples of catalytic reaction involving the 1,5-
hydrogen shift to the vinylidene α-carbon atom, see: (a) Tobisu, M.;
Nakai, H.; Chatani, N. Platinum and Ruthenium Chloride-Catalyzed
Cycloisomerization of 1-Alkyl-2-ethynylbenzenes: Interception of π-
Activated Alkynes with a Benzylic C−H Bond. J. Org. Chem. 2009, 74,
5471−5475. (b) Odedra, A.; Datta, S.; Liu, R.-S. Ruthenium-
Catalyzed Cyclization of 2-Alkyl-1-ethynylbenzenes via a 1,5-Hydro-
gen Shift of Ruthenium−Vinylidene Intermediates. J. Org. Chem.
2007, 72, 3289−3292. (c) Bajracharya, G. B.; Pahadi, N. K.; Gridnev,
I. D.; Yamamoto, Y. PtBr2-Catalyzed Transformation of Allyl(o-
ethynylaryl)carbinol Derivatives into Functionalized Indenes. Formal
sp3 C−H Bond Activation. J. Org. Chem. 2006, 71, 6204−6210.
(d) Datta, S.; Odedra, A.; Liu, R.-S. Ruthenium-Catalyzed Cyclo-
isomerization of cis-3-En-1-ynes to Cyclopentadiene and Related
Derivatives through a 1,5-Sigmatropic Hydrogen Shift of Ruthenium−
Vinylidene Intermediates. J. Am. Chem. Soc. 2005, 127, 11606−11607.
See also ref 9a,b, and e.
(6) Hao, L.; Hong, J.-J.; Zhu, J.; Zhan, Z.-P. One-Pot Synthesis of
Pyrazoles through a Four-Step Cascade Sequence. Chem. - Eur. J.
2013, 19, 5715−5720.
(7) Fukumoto, Y.; Daijo, M.; Chatani, N. Rhenium-Catalyzed Regio-
and Stereoselective Addition of Imines to Terminal Alkynes Leading
to N-Alkylideneallylamines. J. Am. Chem. Soc. 2012, 134, 8762−8765.
(8) For recent reviews on catalytic reactions involving the
vinylidenemetal complex as the key intermediate, see: (a) Varela, J.
́
́
A.; Gonzalez-Rodríguez, C.; Saa, C. Catalytic Transformations of
Alkynes via Ruthenium Vinylidene and Allenylidene Intermediates. in
Topics in Organometallic Chemistry, Vol. 48; Dixneuf, P. H.; Bruneau,
C., Eds; Springer: Basel, 2014; pp 237−287. (b) Metal Vinylidenes and
Allenylidenes in Catalysis: From Reactivity to Applications in Synthesis;
Dixneuf, P. H., Bruneau, C., Eds.; Wiley-VCH: Weinheim, 2008.
(c) Trost, B. M.; McClory, A. Metal Vinylidenes as Catalytic Species
in Organic Reactions. Chem. - Asian J. 2008, 3, 164−194.
(15) Ouh, L. L.; Muller, T. E.; Yan, Y. K. Intramolecular
̈
Hydroamination of 6-Aminohex-1-yne Catalyzed by Lewis Acidic
Rhenium(I) Carbonyl Complexes. J. Organomet. Chem. 2005, 690,
3774−3782.
(9) For other examples of catalytic reaction involving the
vinyldenerhenium complexes as the key intermediate: (a) Chen, J.;
Wu, J. Catalytic Vinylogous Cross-Coupling Reactions of Rhenium
Vinylcarbenoids. Chem. Sci. 2018, 9, 2489−2492. (b) Iwasawa, N.;
Watanabe, S.; Ario, A.; Sogo, H. Re(I)-Catalyzed Hydropropargyla-
tion of Silyl Enol Ethers Utilizing Dynamic Interconversion of
Vinylidene−Alkenylmetal Intermediates via 1,5-Hydride Transfer. J.
Am. Chem. Soc. 2018, 140, 7769−7772. (c) Murai, M.; Uemura, E.;
Takai, K. Amine-Promoted anti-Markovnikov Addition of 1,3-
Dicarbonyl Compounds with Terminal Alkynes under Rhenium
Catalysis. ACS Catal. 2018, 8, 5454−5459. (d) Murai, M.; Uemura,
E.; Hori, S.; Takai, K. Rhenium-Catalyzed Construction of Polycyclic
Hydrocarbon Frameworks by a Unique Cyclization of 1,n-Diynes
Initiated by 1,1-Difunctionalization with Carbon Nucleophiles. Angew.
Chem., Int. Ed. 2017, 56, 5862−5866. (e) Sogo, H.; Iwasawa, N.
Rhenium(I)-Catalyzed Generation of α,β-Unsaturated Carbene
Complex Intermediates from Propargyl Ethers for the Preparation
of Cycloheptadiene Derivatives. Angew. Chem., Int. Ed. 2016, 55,
(16) (a) Lee, K. F.; Bai, W.; Sung, H. H. Y.; Williams, I. D.; Lin, Z.;
Jia, G. Rhenium-Promoted C-C Bond-Cleavage Reactions of Internal
Propargyl Alcohols. Chem. - Eur. J. 2018, 24, 9760−9764.
(b) Mantovani, N.; Marvelli, L.; Rossi, R.; Bianchini, C.; de los
Rios, I.; Romerosa, A.; Peruzzini, M. Backward Synthesis of
Rhenium(I) γ-Hydroxyvinylidene and γ-Methoxyvinylidene Com-
plexes and Their Conversion to the Allenylidene [Re(C =
C=CPh2)(CO)2{MeC(CH2PPh2)3}](OSO2CF3). J. Chem. Soc., Dal-
ton Trans. 2001, 2353−2361. (c) Albertin, G.; Antoniutti, S.;
Bordignon, E.; Bresolin, D. Reactivity of [Re(η2-H2)(CO)2P3]+
Cations with Alkynes: Preparation of Vinylidene and Propadienyli-
dene Complexes. J. Organomet. Chem. 2000, 609, 10−20.
(d) Dembinski, R.; Lis, T.; Szafert, S.; Mayne, C. L.; Bartik, T.;
Gladysz, J. A. Appreciably Bent sp Carbon Chains: Synthesis,
Structure, and Protonation of Organometallic 1,3,5-Triynes and
1,3,5,7-Tetraynes of the Formula (η5-C5Me5)Re(NO)(PPh3)-
E
Org. Lett. XXXX, XXX, XXX−XXX