Organic Letters
Letter
(
6) For selected reviews on catalytic reductive C−C coupling via
Trimethylstannyl-2-[(trimethylstannyl)methyl]propene, an Isobutene
Dianion Synthetic Equivalent. Synthesis 1991, 1991, 267−269.
(c) D’Aniello, F.; Mattii, D.; Taddei, M. 2-(Chloromethyl)-2-
(trimethylsilyl)-1-propene: A Convenient Reagent for the Synthesis
of Methylenetetrahydrofurans and Methylenebutyrolactones. Synlett
1993, 1993, 119−121. (d) D’Aniello, F.; Mann, A.; Mattii, D.;
Taddei, M. Stereoselective “Ene” Reaction of Allylsilanes with Amino
Aldehydes. An Application to the Synthesis of Potential HIV-1
Protease Inhibitors. J. Org. Chem. 1994, 59, 3762−3768. (e) Ryter, K.;
Livinghouse, T. [2-((Trimethylsilyl)methyl)prop-2-enyl]- lithium. A
Versatile Reagent for the Synthesis of 2-Substituted Propenylsilanes. J.
Org. Chem. 1997, 62, 4842−4844. (f) Kang, K.-T.; Sung, T. M.; Kim,
J. K.; Kwon, Y. M. Synthesis of Functionalized Allylsilanes Using 3-
hydrogenation, transfer hydrogenation, and hydrogen autotransfer,
see: (a) Hassan, A.; Krische, M. J. Unlocking Hydrogenation for C-C
Bond Formation: A Brief Overview of Enantioselective Methods. Org.
Process Res. Dev. 2011, 15, 1236−1242. (b) Ketcham, J. M.; Shin, I.;
Montgomery, T. P.; Krische, M. J. Catalytic Enantioselective C-H
Functionalization of Alcohols by Redox-Triggered Carbonyl Addition:
Borrowing Hydrogen, Returning Carbon. Angew. Chem., Int. Ed. 2014,
5
3, 9142−9150. (c) Nguyen, K. D.; Park, B. Y.; Luong, T.; Sato, H.;
Garza, V. J.; Krische, M. J. Metal-catalyzed reductive coupling of
olefin-derived nucleophiles: Reinventing carbonyl addition. Science
2
016, 354, aah5133. (d) Kim, S. W.; Zhang, W.; Krische, M. J.
Catalytic Enantioselective Carbonyl Allylation and Propargylation via
Alcohol-Mediated Hydrogen Transfer: Merging the Chemistry of
Grignard and Sabatier. Acc. Chem. Res. 2017, 50, 2371−2380.
(
1
Stannyl)-2-(silylmethyl)propene. Synth. Commun. 1997, 27, 1173−
181. (g) Barrett, A. G. M.; Braddock, D. C.; de Koning, P. D.
(
7) For selected reviews on enantioselective carbonyl allylation, see:
Bidirectional Asymmetric Allylboration and The Synthesis of C2
Symmetric 3-Methylenepentane-1,5-Diols. Chem. Commun. 1999,
(
a) Ramachandran, P. V. Pinane-based versatile ″allyl″ boranes.
Aldrichimica Acta 2002, 35, 23−35. (b) Denmark, S. E.; Fu, J.
Catalytic Enantioselective Addition of Allylic Organometallic
Reagents to Aldehydes and Ketones. Chem. Rev. 2003, 103, 2763−
4
59−460. (h) Barrett, A. G. M.; Braddock, D. C.; de Koning, P.
D.; White, A. J. P.; Williams, D. J. Bidirectional Asymmetric
Allylboration. A Convenient Asymmetric Synthesis of C -Symmetric
2
2794. (c) Yu, C.-M.; Youn, J.; Jung, H.-K. Regulation of Stereo-
3
-Methylenepentane-1,5-diols and Rapid Access to C -Symmetric
2
selectivity and Reactivity in the Inter- and Intramolecular Allylic
Transfer Reactions. Bull. Korean Chem. Soc. 2006, 27, 463−472.
d) Marek, I.; Sklute, G. Creation of quaternary stereocenters in
carbonylallylation reactions. Chem. Commun. 2007, 1683−1691.
e) Hall, D. G. Lewis and Brønsted Acid Catalyzed Allylboration of
Spiroketals. J. Org. Chem. 2000, 65, 375−380. (i) Yu, C.-M.; Lee, J.-
Y.; So, B.; Hong, J. Sequential Catalytic Asymmetric Allylic Transfer
Reaction: Enantioselective and Diastereoselective Construction of
Tetrahydropyran Units. Angew. Chem., Int. Ed. 2002, 41, 161−163.
(
(
(
j) Keck, G. E.; Yu, T.; McLaws, M. D. Enantio- and
Carbonyl Compounds: From Discovery to Mechanism and
Applications. Synlett 2007, 2007, 1644−1655. (f) Hargaden, G. C.;
Guiry, P. J. The Development of the Asymmetric Nozaki−Hiyama−
Kishi Reaction. Adv. Synth. Catal. 2007, 349, 2407−2424.
Diastereoselective Additions to Aldehydes Using the Bifunctional
Reagent 2-(Chloromethyl)-3-(tributylstannyl)propene: Application to
a Synthesis of the C16-C27 Segment of Bryostatin 1. J. Org. Chem.
2005, 70, 2543−2550. (k) Heumann, L. V.; Keck, G. E. A. A New
(
g) Lachance, H.; Hall, D. G. Allylboration of Carbonyl Compounds.
Construction of 2-Alkoxypyrans by an Acylation-Reductive Cycliza-
tion Sequence. Org. Lett. 2007, 9, 1951−1954. (l) Trost, B. M.;
Bringley, D. A.; Silverman, S. M. Asymmetric Synthesis of
Methylenetetrahydrofurans by Palladium-Catalyzed [3 + 2] Cyclo-
addition of Trimethylenemethane with Aldehydes − A Novel Ligand
Design. J. Am. Chem. Soc. 2011, 133, 7664−7667. (m) Williams, D.
R.; Claeboe, C. D.; Liang, B.; Zorn, N.; Chow, N. S. C. A
Org. React. 2009, 73, 1−596. (h) Han, S. B.; Kim, I. S.; Krische, M. J.
Enantioselective iridium-catalyzed carbonyl allylation from the alcohol
oxidation level via transfer hydrogenation: minimizing pre-activation
for synthetic efficiency. Chem. Commun. 2009, 7278−7287. (i) Yus,
M.; Gonzal
Allylation of Carbonyl Compounds and Imines. Chem. Rev. 2011, 111,
774−7854. (j) Moran, J.; Krische, M. J. Enantioselective Carbonyl
ez-Gomez, J. C.; Foubelo, F. Catalytic Enantioselective
́ ́
7
Bidirectional S ′ Strategy for 1,5-syn and 1,5-anti Stereocontrol
E
Allylation and Crotylation from the Alcohol Oxidation Level via C-C
Bond Forming Transfer Hydrogenation. Asymmetric Synthesis Ii: More
Methods and Applications 2013, 187−196. (k) Yus, M.; Gonzalez-
Gomez, J. C.; Foubelo, F. Diastereoselective Allylation of Carbonyl
Compounds and Imines: Application to the Synthesis of Natural
Products. Chem. Rev. 2013, 113, 5595−5698. (l) Huo, H.-X.; Duvall,
J. R.; Huang, M.-Y.; Hong, R. Catalytic asymmetric allylation of
carbonyl compounds and imines with allylic boronates. Org. Chem.
Front. 2014, 1, 303−320. (m) Kumar, P.; Tripathi, D.; Sharma, B. M.;
Dwivedi, N. Transition metal catalysisa unique road map in the
stereoselective synthesis of 1,3-polyols. Org. Biomol. Chem. 2017, 15,
toward the Synthesis of Complex Polyols. Org. Lett. 2012, 14, 3866−
3
869. (n) Ahlers, A.; de Haro, T.; Gabor, B.; Furstner, A. Concise
̈
Total Synthesis of Enigmazole A. Angew. Chem., Int. Ed. 2016, 55,
1
406−1411. (o) Tekle-Smith, M. A.; Williamson, K. S.; Hughes, I. F.;
Leighton, J. L. Direct, Mild, and General n-Bu NBr-Catalyzed
4
Aldehyde Allylsilylation with Allyl Chlorides. Org. Lett. 2017, 19,
6
(
024−6027.
11) For the synthesis of 4-methylenepyrrolidines via TMM-imine
cycloaddition, see: (a) Jones, M. D.; Kemmitt, R. D. W. J. Reactions
between Trimethylenemethane Metal Complexes and The Carbon−
Nitrogen Double Bond: Nickel and Palladium Catalysed Synthesis of
Pyrrolidines. J. Chem. Soc., Chem. Commun. 1986, 1201−1203.
7
33−761. (n) Spielmann, K.; Niel, G.; de Figueiredo, R. M.;
Campagne, J. M. Catalytic nucleophilic ‘umpoled’ π-allyl reagents.
Chem. Soc. Rev. 2018, 47, 1159−1173.
(
(
3
b) Trost, B. M.; Marrs, C. M. A [3 + 2] Cycloaddition and [4 +
] Cycloaddition Approach to N-Heterocycles via Palladium-
Catalyzed TMM Reactions with Imines. J. Am. Chem. Soc. 1993,
8) For a related approach to the asymmetric synthesis of substituted
pyrans, see: Shin, I.; Wang, G.; Krische, M. J. Catalyst-Directed
Diastereo- and Site-Selectivity in Successive Nucleophilic and
Electrophilic Allylations of Chiral 1,3-Diols: Protecting Group-Free
Synthesis of 4-Hydroxy-2,6-cis- or trans-Pyrans. Chem. - Eur. J. 2014,
1
15, 6636−6645. (c) Trost, B. M.; Silverman, S. M.; Stambuli, J. P.
Palladium-Catalyzed Asymmetric [3 + 2] Cycloaddition of
Trimethylenemethane with Imines. J. Am. Chem. Soc. 2007, 129,
12398−12399. (d) Trost, B. M.; Silverman, S. M. Enantioselective
2
(
0, 13382−13389.
Construction of Highly Substituted Pyrrolidines by Palladium-
Catalyzed Asymmetric [3 + 2] Cycloaddition of Trimethylene-
methane with Ketimines. J. Am. Chem. Soc. 2010, 132, 8238−8240.
(e) Trost, B. M.; Silverman, S. M. Enantioselective Construction of
Pyrrolidines by Palladium-Catalyzed Asymmetric [3 + 2] Cyclo-
addition of Trimethylenemethane with Imines. J. Am. Chem. Soc.
2012, 134, 4941−4954. (f) Trost, B. M.; Lam, T. M.; Herbage, M. A.
Regio- and Enantioselective Synthesis of Pyrrolidines Bearing a
Quaternary Center by Palladium-Catalyzed Asymmetric [3 + 2]
Cycloaddition of Trimethylenemethanes. J. Am. Chem. Soc. 2013, 135,
2459−2461.
9) During the preparation of our manuscript, there appeared a
report on the use of our π-allyliridium-C,O-benzoate catalysts in
bidirectional carbonyl allylations using 3-chloro-2-chloromethyl-1-
propene: Quintard, A.; Rodriguez, J. Enantioselective Ir-Catalyzed
Bidirectional Reductive Coupling. Org. Lett. 2019, 21, 453−456.
(
10) For selected examples of related bifunctional reagents
incorporating allylstannane, allylborane, or allylsilane moieties, see:
a) Trost, B. M.; King, S. A. A Two Catalyst System for Cycloadditlon
of a Trimethylenemethane Fragment to Aldehydes. Tetrahedron Lett.
986, 27, 5971−5974. (b) Degl’Innocenti, A.; Dembech, P.; Mordini,
A.; Ricci, A.; Seconi, G. [3 + n] Annulation Reactions by Means of 3-
(
1
D
Org. Lett. XXXX, XXX, XXX−XXX